Drell-Yan processes, transversity and light-cone wavefunctions
FactSage_热力学计算在耐火材料抗渣侵蚀性中的应用
第43卷第3期2024年3月硅㊀酸㊀盐㊀通㊀报BULLETIN OF THE CHINESE CERAMIC SOCIETY Vol.43㊀No.3March,2024FactSage 热力学计算在耐火材料抗渣侵蚀性中的应用郭伟杰1,2,朱天彬1,2,李亚伟1,2,廖㊀宁1,2,桑绍柏1,2,徐义彪1,2,鄢㊀文1,2(1.武汉科技大学省部共建耐火材料与冶金国家重点实验室,武汉㊀430081;2.武汉科技大学高温材料与炉衬技术国家地方联合工程研究中心,武汉㊀430081)摘要:商用热力学计算软件FactSage 在耐火材料抗渣侵蚀性研究中起到重要作用,因此在耐火材料研究中应用越来越广泛㊂本文总结了近15年来热力学计算在耐火材料抗渣侵蚀性研究中的应用,重点介绍了耐火材料抗渣侵蚀研究中常用的热力学计算模型,分析了各种模型的原理㊁特点㊁适用情景㊁精确度与局限性,并给出了详细的运用实例㊂此外,本文介绍了热力学计算与其他方法相结合运用的实例,包含ANSYS㊁动力学分析㊁分子动力学模拟等方法,规避热力学计算的局限性,更加全面地分析熔渣对耐火材料的侵蚀行为㊂最后,本文对热力学计算存在的问题进行了归纳,并基于现有研究现状对其发展前景与方向进行了展望㊂关键词:耐火材料;热力学计算;抗渣侵蚀性;FactSage;热力学模型中图分类号:TQ175㊀㊀文献标志码:A ㊀㊀文章编号:1001-1625(2024)03-1110-13Application of FactSage Thermodynamic Calculation on Slag Corrosion Resistance of RefractoriesGUO Weijie 1,2,ZHU Tianbin 1,2,LI Yawei 1,2,LIAO Ning 1,2,SANG Shaobai 1,2,XU Yibiao 1,2,YAN Wen 1,2(1.The State Key Laboratory of Refractories and Metallurgy,Wuhan University of Science and Technology,Wuhan 430081,China;2.National-Provincial Joint Engineering Research Center of High Temperature Materials and Lining Technology,Wuhan University of Science and Technology,Wuhan 430081,China)Abstract :Commercial thermodynamic calculation software FactSage plays an important role in the analysis of slag corrosion process,therefore it has been widely used in the research of refractories.Application of thermodynamic calculation on slag corrosion resistance of refractories and thermodynamic calculation models which are commonly used in the slag corrosionresistance of refractories were introduced.The mechanisms,characteristics,applicable situations,accuracy and limitations of every model were discussed,and the detailed examples were given.Furthermore,the application examples of FactSage combined with other methods including ANSYS,kinetic analysis and MD simulation were given,aiming to avoid the limitations of thermodynamic calculation and comprehensively analyze the slag corrosion stly,the common problems of thermodynamic calculation were summarized,and the direction of further development was proposed.Key words :refractory;thermodynamic calculation;slag corrosion resistance;FactSage;thermodynamic model 收稿日期:2023-09-27;修订日期:2023-12-06基金项目:国家自然科学基金联合基金重点项目(U21A2058,U1908227,52272071);湖北省自然科学基金项目(2022CFB024)作者简介:郭伟杰(1998 ),男,硕士研究生㊂主要从事耐火材料抗渣性能的研究㊂E-mail:1099255596@通信作者:朱天彬,博士,副教授㊂E-mail:zhutianbin@ 0㊀引㊀言随着计算机技术的高速发展,集成了大量热力学数据的商用热力学计算软件成为研究者的重要工具㊂FactSage [1]最早于1976年提出,2001年加拿大蒙特利尔综合工业大学的FACT-win 软件与德国GTT 公司的ChemSage 软件整合为FactSage,这是目前应用最为广泛的热力学计算软件之一㊂该软件集成了大量热力学数据库,包括溶液㊁化合物㊁纯物质㊁熔盐㊁合金的数据,并整合了以多元相平衡计算为代表的多种功能,是一㊀第3期郭伟杰等:FactSage热力学计算在耐火材料抗渣侵蚀性中的应用1111个综合性集成热力学计算软件[2-3],已在全球800多所大学㊁实验室和企业中应用[4]㊂在耐火材料领域,FactSage热力学计算同样占据着重要地位,已被应用于相图绘制㊁熔渣侵蚀分析㊁液相含量分析㊁黏度计算㊁复杂条件下多元多相体系平衡㊁体系热力学函数计算等诸多方面[5-8]㊂其中,热力学计算能够较好地分析耐火材料抗渣侵蚀性,在熔渣性质㊁热力学平衡相㊁液相组成等方面提供重要参考㊂因此,本文综述了近15年来FactSage热力学计算在耐火材料抗渣侵蚀研究进展,给出了基于热力学计算的抗渣侵蚀性研究案例,以期为相关科研工作者使用热力学计算分析耐火材料抗渣侵蚀机理提供参考和借鉴㊂同时,基于近年来的研究现状,总结FactSage热力学计算在耐火材料抗渣侵蚀性的发展趋势,并对其发展前景进行了展望㊂1㊀耐火材料抗渣侵蚀研究中的热力学计算模型热力学计算中,FactSage的Equilib模块是模拟熔渣与耐火材料反应过程的最常用工具㊂该模块通过原ChemSage的算法,基于吉布斯自由能最低原理[9-10],能够较好地预测熔渣对耐火材料侵蚀过程中的热力学平衡相与液相组成变化㊂使用该模块进行耐火材料抗渣侵蚀性研究的常用过程如图1所示㊂图1㊀使用FactSage的Equilib模块对熔渣-耐火材料侵蚀过程进行分析的主要步骤Fig.1㊀Main steps during the analysis of slag corrosion resistance of refractories using Equilib module of FactSage选择合适的热力学计算模型是获取准确的热力学计算结果的前提㊂不同的热力学计算模型具有不同的侧重点,应当基于当前研究体系的特点,选取合适的模型以达到较好的模拟效果㊂目前,经过国内外研究者的长期研究,以界面反应模型为代表的热力学计算模型被广泛开发,并经过了大量实验验证,具有较高的准确度与可信度㊂下面对常用的热力学计算模型分别进行介绍㊂1.1㊀物相-温度模型图2为物相-温度模型的示意图㊂物相-温度模型是一种常用的计算模型,能够较好地反映物相随温度的变化情况㊂物相-温度模型的示意图如图2(a)所示,熔渣与耐火材料的质量恒定(常设定为100gʒ100g),在该模型中温度是唯一的变量,通过计算得到物相-温度曲线(见图2(b)),从而反映物相随温度的变化过程㊂该模型常用于分析温度对耐火材料抗渣侵蚀性的影响以及高熔点相在耐火材料内的生成温度等情况㊂此外,该模型变量较少㊁上手门槛较低,适用于大多数耐火材料抗渣侵蚀性分析㊂图2㊀物相-温度模型的示意图Fig.2㊀Schematic diagram of phase-temperature thermodynamic model在Gehre等[11]关于含硫渣对尖晶石耐火材料的侵蚀行为的研究中,通过设定30g熔渣与10g耐火材料在强还原气氛下进行反应,得到了尖晶石㊁CaMg2Al16O27相在800~1450ħ的变化趋势(见图3),较好地描述了固相随温度降低逐渐析出的过程㊂类似地,在刚玉尖晶石浇注料体系中,Ramult等[12]在1112㊀耐火材料硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷图3㊀矿物相与熔渣含量与温度的函数关系[11]Fig.3㊀Functional relationship between mineral phase,slag content and temperature [11]1200~1700ħ设定50%(文中均为质量分数)耐火材料与50%钢渣反应,比较了三种不同碱度的熔渣对浇筑料侵蚀后的产物区别㊂该方法同样在铜工业用无铬耐火材料中运用,Jastrzębska 等[13]通过将50g 的不同种类铜渣与50g 的Al 2O 3-MgAl 2O 4耐火材料进行计算,发现尖晶石能够在较大温度范围内稳定存在,证实了该种耐火材料对铜渣具有较好的抵抗能力㊂而在炉渣的固相分数分析中,Anton 等[14]则使用该模型计算了熔渣的完全融化温度,发现碱度不随固体析出而变化㊂物相-温度模型对熔渣-耐火材料体系内固相的析出温度具有良好的精确度,并能够准确判断固相在高温下的稳定情况,且可以确定产生液相的温度点㊂此外,这种热力学模型以温度作为变量,适合于描述较大温度范围内的熔渣侵蚀情况,能够提供从升温到降温的全过程熔渣侵蚀产物分析㊂然而,该种模型具有明显的局限性㊂众所周知,熔渣侵蚀耐火材料的过程中,熔渣含量变化导致系统物相组成不断变化,熔渣侵蚀耐火材料的过程是一个渐进的过程㊂使用温度-物相模型时,由于熔渣与耐火材料组分未引入变量,采用了固定值进行计算,导致其计算结果是对熔渣侵蚀最终结果的预测,而无法渐进㊁全面地展现熔渣对耐火材料的侵蚀过程㊂侵蚀过程描述的缺失使得中间相的产生机理无法较好地被描述(如浇注料体系中二铝酸钙(CA 2)与六铝酸钙(CA 6)相的含量变化),导致复杂体系的精确度较差㊂1.2㊀溶解模型图4为溶解模型示意图,图5为不同气氛下镁铬耐火材料-冰铜渣系统的热力学平衡相㊂溶解模型也是耐火材料抗渣侵蚀研究中一种常用的模型,如图4(a)所示,该模型设定耐火材料的质量恒定不变,熔渣质量线性增加㊂在该模型中,定义质量比A =m S /m R (m S 为熔渣质量,m R 为耐火材料质量),对系统内各组分使用表达式<m R +m S ˑA >进行描述,即随着A 值的增加,在耐火材料质量不变的情况下,熔渣质量从0开始不断线性增加,从而模拟熔渣量从少到多的侵蚀过程㊂如图4(b)所示,该模型较好地反映了组分在熔渣内的溶解速率情况与稳定程度,通过物相质量-A 曲线的斜率定性反映溶解速率,通过曲线归零时所需A 的绝对值反映该物相在熔渣内的稳定程度㊂图4㊀溶解模型示意图Fig.4㊀Schematic diagrams of dissolution model 溶解模型由于具有较好的普适性而被广泛运用于耐火材料抗渣侵蚀研究中㊂在Liu 等[15]㊁王恭一等[16]和程艳俏等[17]针对镁铬质耐火材料抗渣侵蚀性的研究中,根据如图5所示的热力学计算,发现镁铬尖晶石㊁镁铁尖晶石以及镁橄榄石在系统内可以稳定存在;而在还原气氛下(见图5(b)),镁橄榄石的含量明显下㊀第3期郭伟杰等:FactSage热力学计算在耐火材料抗渣侵蚀性中的应用1113降,且生成了Pb(g),从而解释了还原气氛下耐火材料抗渣侵蚀性下降的原因㊂在评价耐火骨料抗渣侵蚀性的研究中,金胜利等[18]分别计算了高炉钛渣对棕刚玉㊁电熔刚玉㊁亚白刚玉㊁镁铝尖晶石以及特级矾土的侵蚀,通过比较刚玉相完全消失时的A值分析了五种常见骨料的抗侵蚀能力㊂桑绍柏等[19]通过热力学计算发现SiC能够与含Ti熔渣反应生成稳定的FeSi与TiC相,且SiC在A=4.5时才完全消耗,证明了SiC在该体系内具有良好的稳定性㊂吕晓东等[20]通过该模型计算发现SiC㊁钛尖晶石在钛渣中具有较好的稳定性,这与静态坩埚法得到的结果一致㊂马三宝等[21]也计算了钢包渣对轻质方镁石-尖晶石耐火材料的侵蚀,得出尖晶石的溶解速率大于方镁石㊂而李真真等[22]使用该模型研究了氧化钛对镁砂抗渣渗透性能的影响,发现生成的CaTiO3在熔渣内比镁砂更加稳定㊂图5㊀不同气氛下镁铬耐火材料-冰铜渣系统的热力学平衡相[15]Fig.5㊀Equilibrium phases of magnesia chromite refractories-matte slag system under different atmospheres[15]该模型对高熔点物相在熔渣体系内的稳定度预测展现出较为良好的精确度㊂由于该模型中引入了变量A=m S/m R,特定物相消失时的A值反映了该物相在熔渣内的稳定程度,因此该模型能够较好地发现特定熔渣体系内的高熔点相(如尖晶石相㊁CaTiO3相与方镁石相),为针对性地开发具有优异抗渣侵蚀性的耐火材料提供依据㊂并且,该种模型能够有效地对比不同耐火材料体系在特定熔渣下的稳定程度,从而针对酸性渣㊁碱性渣㊁富钛渣㊁富锰渣等不同熔渣体系挑选对应的耐火材料,满足特定条件的需求㊂然而,该种模型仍具有一定局限性,虽然能够良好地预测高熔点㊁高稳定相的生成,却缺乏定性地描述这些物相在侵蚀区域相对位置的能力,例如其能够精确地预测刚玉骨料外侧生成CA2与CA6相,但难以定性地描述两相在骨料外侧的位置㊂因此,使用该种模型时需结合SEM㊁EDS等表征手段进行深入分析㊂此外,在真实的熔渣侵蚀过程中,由于耐火材料组分向熔渣中逐渐溶解,熔渣的组分受到耐火材料的影响而不断改变,因此熔渣组分处于 不断更新 的状态㊂而该模型中熔渣组分恒定不变,即恒定保持初始化学组分㊁仅逐步提升熔渣的质量,无法精确地描述熔渣与耐火材料之间的组分交换㊂因此,该种模型适合对静态坩埚抗渣法等熔渣组分变化不大的情景进行分析,对感应炉抗渣㊁回转窑抗渣㊁钢包渣线抗渣等组分交换剧烈㊁熔渣处于动态情景的模拟精确度较低㊂1.3㊀界面反应模型界面反应模型能够有效地模拟熔渣-耐火材料界面处的相互作用过程,被广泛应用于多种耐火材料体系中,其计算结果经过了广泛验证,是目前常用㊁可信的模型之一㊂该模型最早由Berjonneau等[23]于2009年提出,最初用于模拟恒定温度㊁压力条件下二次冶金钢包渣对Al2O3-MgO耐火材料的侵蚀㊂界面反应模型的示意图如图6所示,在该模型中定义了反应度B=w R/(w S+w R),并满足w R+w S=1,其中w R为耐火材料质量分数,w S为熔渣的质量分数,对系统内的组分采用表达式<m S-(m S-m R)ˑB>进行描述㊂B反映了耐火材料-熔渣界面的反应程度,当B接近0时,系统中熔渣比例较高,反应程度较低,反之B接近1时,系统中耐火材料占比较高,反应程度越高㊂如图6(b)所示,反应度B可以近似为熔渣-耐火材料接触的界面层的相对位置,B趋近于1时,生成的物相越接近耐火材料表层,而其趋近于0时物相靠近熔渣侧㊂这一特性使得该模型能较好地反映了侵蚀过程中固相的相对位置与生成量,因此尤其适合模拟保护层的生成情况㊂1114㊀耐火材料硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷图6㊀界面反应模型的示意图[21]Fig.6㊀Schematic diagrams of interlayer reaction model[21]溶解模型在耐火材料抗渣领域得到了广泛应用,并被大量实验证明具有良好的精确度㊂Berjonneau 等[23]通过实验验证了该模型的精确度,计算结果与实际侵蚀区域的微观结构呈良好的对应关系(见图7(a)),并得出了CA2和CA6相的形成机理(图7(b))㊂Tang等[24]使用该模型对Al2O3坩埚的侵蚀行为进行了分析和实验验证,发现热力学计算预测的熔渣㊁CA2㊁CA6㊁尖晶石以及刚玉骨料的位置与实际实验结果一致㊂在蒋旭勇等[25]的研究中,通过该模型计算了铝镁质浇注料对不同Al2O3含量的CaO-SiO2-Al2O3渣的物相生成量,发现高Al2O3含量的熔渣能够促进形成更厚的隔离层㊂在高纯度镁质耐火材料对富铁渣的抗渣侵蚀性研究中,Betsis等[26]利用该模型发现,富铁渣将方镁石转化为MgO-Fe x O,且发现液相中FeO含量上升㊂类似地,Oh等[6]也观测到了MgO-Fe x O层,且MgO㊁FeO相对含量与显微结构观察一致㊂李艳华等[27]使用该模型对LF渣对ρ-Al2O3结合铝镁质浇注料的侵蚀行为进行了分析,通过FactSage软件得到了尖晶石的组成,结果显示生成的尖晶石中含有一定量的MnAl2O4和FeAl2O4,即熔渣中的Mn2+㊁Fe2+生成了复合尖晶石㊂Guo等[28]使用该模型计算了熔渣侵蚀钙镁铝酸盐(CMA)骨料产生的热力学平衡相,发现CMA骨料内的一铝酸钙(CA)㊁CA2相在高温下转化为液相,提高了熔渣的Al2O3含量㊂图7㊀熔渣对刚玉骨料的侵蚀的热力学计算结果[21]Fig.7㊀Thermodynamic calculation results of corrosion of slag to corundum aggregate[21]㊀第3期郭伟杰等:FactSage热力学计算在耐火材料抗渣侵蚀性中的应用1115溶解模型不仅可以预测物相组成的变化,还常用于预测熔渣侵蚀过程中液相组成的变化与黏度变化[29]㊂Wang等[30]使用该模型对ZrO2耐火材料对高碱度精炼渣的侵蚀行为进行了研究,图8为ZrO2耐火材料的侵蚀过程的热力学计算结果㊂EDS线扫描中ZrO2含量从耐火材料到过渡层逐渐降低,CaO含量随着渣层到过渡层逐渐降低,其趋势与热力学计算结果一致㊂鄢文等[31]研究了熔渣对刚玉尖晶石浇注料侵蚀的热力学模型,结果显示,侵蚀层到耐火材料内部SiO2㊁CaO含量逐渐降低,而SiO2的含量则先降低后增加,这与A值介于0.66至0.84之间的曲线相吻合㊂此外,Peng等[32]计算了轻质方镁石-尖晶石浇注料与熔渣反应过程中的液相黏度变化,证明了该种耐火材料优秀的抗渣渗透性能㊂图8㊀ZrO2耐火材料侵蚀过程的热力学计算结果[27]Fig.8㊀Thermodynamic calculation results of corrosion process of ZrO2refractories[27]作为最常用的抗渣模型之一,界面反应模型最大的优势为能够生动地描述物相的生成机理㊁生成位置㊂由于变量B=w R/(w S+w R)的引入,界面反应模型能够细致地描述熔渣对耐火材料侵蚀的全过程,详细地展现各热力学平衡相的含量变化,其良好的精确度与泛用性使得其被广大研究者所使用,助力了许多研究成果的产出,并得到了广泛的实验验证㊂然而,该模型同样具有一定的局限性㊂如前文所述,熔渣对耐火材料侵蚀是一个动态的过程,渣组分会随侵蚀程度的改变不断变化,Zhang等[33]指出,该模型忽略了耐火材料溶解对熔渣化学组分变化,使得其对动态渣蚀的模拟存在一定的误差㊂在真实熔渣侵蚀过程中,耐火材料的损毁常是由溶解㊁化学反应与渗透共同导致的㊂该模型虽然能够较好地描述熔渣-耐火材料界面上的化学反应,却不能很好地胜任熔渣渗透过程的模拟㊂此外,受制于热力学计算的局限性,界面反应模型无法展现耐火材料表面形貌㊁扩散速率㊁熔体冲刷等因素对抗渣侵蚀性的影响㊂1.4㊀逐步迭代模型在实际侵蚀过程中,熔渣化学组分会随着熔渣与耐火材料的反应而发生变化,从而影响熔渣的侵蚀能力,而溶解模型与界面反应模型忽略了这一变化,且两者均不能较好地模拟熔渣的渗透过程㊂针对以上问题,Luz等[34]设计了一个新的模型,迭代模型的示意图如图9所示㊂该模型具有一个迭代程序,其原理如图9(a)所示,设定第一反应阶段初始耐火材料质量与熔渣质量均为100g(S为熔渣,R为耐火材料),将反应后将得到的改性渣(S1)再次与相同质量的耐火材料进行二次迭代计算得到新的改性渣(S2),不断重复该过程直至熔渣量归零或达到饱和,通过该迭代程序,每一次循环后熔渣组分都会改变㊂该模型同样可以用于描述熔渣对耐火材料的渗透过程(图9(b)),即更大的迭代计算次数对应更长的熔渣渗透距离[31]㊂Calvo等[35]在钢包用铝碳质耐火材料的用后分析中使用该模型分析了熔渣对耐火材料的渗透,其热力学计算结果与用后耐火材料的显微结构如图10所示(MA为镁铝尖晶石)㊂热力学计算结果显示,随着熔渣渗透深度的增加,尖晶石和六铝酸钙将会依次生成㊂从侵蚀区图像中可以看出,从工作面到耐火材料内部依次为镁铝尖晶石㊁二铝酸钙和六铝酸钙,基本与热力学计算一致㊂类似地,在Muñoz等[36]对铝镁碳耐火材料抗渣侵蚀性研究中,该模型计算结果与熔渣渗透区的显微结构吻合程度较高㊂此外,该模型仍可以较为精确1116㊀耐火材料硅酸盐通报㊀㊀㊀㊀㊀㊀第43卷地预测物相的生成情况,并非专用于描述熔渣对耐火材料的渗透情况㊂在Luz等[37]针对尖晶石浇注料的熔渣侵蚀研究中,该模型预测了CA2和CA6相的存在,并通过显微结构验证了热力学计算的准确性㊂Han 等[38]使用该模型计算得到了MgO-Fe x O层,这与侵蚀后试样的显微结构一致㊂在Luz等[39]对镁碳质耐火材料的抗渣侵蚀的研究中,通过该模型计算发现MgO溶解量随着熔渣碱度降低而增加,证明了低碱度渣对镁碳质耐火材料的侵蚀更加强烈㊂图9㊀迭代模型的示意图[31]Fig.9㊀Schematic diagram of the iterative corrosion model[31]图10㊀用后铝碳质耐火材料的热力学计算结果[32]Fig.10㊀Thermodynamic calculation results of spent Al2O3-C refractories[32]与溶解模型㊁界面反应模型相比,迭代模型能够模拟耐火材料组分对熔渣侵蚀能力的影响㊂每次迭代时,熔渣组分都会被耐火材料所改变,改性渣再次与新的耐火材料反应,这个过程模拟熔渣组分更新,因此该模型对动态渣蚀具有更加良好的模拟精确度㊂此外,该种模型能够定性地描述渗透过程,反映熔渣渗透过程中熔渣组分的变化与物相的变化,从而为耐火材料用后分析㊁熔渣渗透行为分析提供重要的参考㊂在真实的熔渣渗透过程中,熔渣的渗透行为除了受到熔渣的组分和黏度的影响外,还会受到接触角㊁气孔孔径㊁晶界渗透㊁渗透时间等诸多因素的影响,而该模型仅能从热力学的角度预测熔渣组分变化㊁黏度变化和物相变化,对物理过程缺乏描述的能力㊂因此将该模型用于描述熔渣渗透过程时,迭代次数仅能够定性地反映渗透深度,不能够精确地给出渗透距离㊂此外,随着熔渣深入耐火材料内部,耐火材料工作面与内部之间的温度梯度也会影响熔渣的渗透行为,而该种模型设定耐火材料内外温度恒定,导致对耐火材料深处的物相的预测存在一定的偏差㊂并且,该种模型中引入了迭代程序,使得计算量大幅增加,部分体系中甚至需要十几次以上的循环计算才能使熔渣完全耗尽或达到饱和,对模型使用者造成了较重的负担㊂这些因素制约了该模型的普及与发展,因此较少研究使用该种模型进行热力学模拟㊂1.5㊀其他热力学计算模型除上述四种最常用的热力学计算模型外,国内外研究者针对不同熔渣侵蚀过程的特点,针对性地开发了新的热力学计算模型,从而更加精确地预测耐火材料侵蚀过程㊂㊀第3期郭伟杰等:FactSage热力学计算在耐火材料抗渣侵蚀性中的应用1117针对迭代模型的局限性,Sagadin等[40]使用FactSage与SimuSage[41]开发了一种新型耐火材料侵蚀模型,用于模拟镍铁渣对镁质耐火材料的侵蚀,并对气孔率和温度梯度的影响进行了模拟,具体如图11所示㊂如图11(a)所示,该模型将耐火材料分为了十个区域,温度从外到内线性递减,每个区域均含有定量的耐火材料与气孔㊂图11(b)为该模型单个区域的运算流程,耐火材料与熔渣首先进行计算,产物被 物相分离器 分离为固体与熔体㊂由于耐火材料的气孔仅能允许一部分熔渣向深处渗透,因此研究者使用SimuSage设计了 熔体分离器 ,将熔体分离为可以进入下一区域的熔体A与被阻碍在该区域的熔体B㊂熔体B与固体氧化物组成混合体并在该区域内再次计算,而熔体A则进入下一区域㊂该模型不仅能够描述熔渣化学组分的变化,还考虑了耐火材料气孔率对熔渣渗透的影响[42]㊂并且,由于温度梯度的存在,橄榄石等能够在材料深处的低温区域稳定存在,这在恒定温度的模型中是无法实现的㊂图11㊀基于FactSage与SimuSage的耐火材料侵蚀模型[37]Fig.11㊀Corrosion model based on FactSage and SimuSage[37]在感应炉抗渣法中,熔渣由于电磁场的作用剧烈地冲刷耐火材料,熔渣的组分由于耐火材料的损毁和熔渣的对流运动而不断混合和改变,并且耐火材料基质与骨料的侵蚀速率不同,导致两者对熔渣组分的改变能力不同,因此需要新的热力学计算模型描述动态条件下的熔渣侵蚀过程㊂在轻量化MgO-Al2O3浇注料的抗渣侵蚀性研究中,邹阳[43]提出了一种新的热力学计算模型,这种模型中熔渣组分受到耐火材料侵蚀的影响,并可以反映骨料与基质的侵蚀速率差别㊂该模型将熔渣侵蚀过程分为了n个相等的时间段,在每个Δt内,熔渣分别与骨料㊁基质进行计算,得到新的液相加和,即为 更新 后的熔渣组分㊂图12为动态熔渣侵蚀下的热力学计算模型㊂相较于其他模型,该模型能够形象地显示骨料㊁基质抗侵蚀能力的差异,且由于受到了骨料㊁基质的共同影响而不断 更新 ,其具有更高的精确度,更加符合动态熔渣条件下熔渣受到对流而不断混合的实际情况㊂图12㊀动态熔渣侵蚀下的热力学计算模型[40]Fig.12㊀Thermodynamic calculation model of dynamic slag corrosion condition[40]综合来看,以上模型在现有的经典模型基础上进行了一定程度的改进,使之能够更好地描述熔渣侵蚀过程,展现熔渣侵蚀模型的改进潜力㊂然而,这些改进模型计算方式复杂,或需要使用其他软件,导致其难以掌握㊂同时,这些模型提出较晚,未在大量研究中被广泛使用,缺乏实验数据的验证㊂受制于热力学计算本身的局限性,这些模型还是仅能从热力学角度描述化学反应过程㊁物相变化,对湍流㊁扩散等现象造成的影响无法给出预测㊂。
DX Image Process
Elsevier items and derived items © 2008 by Mosby, Inc., an affiliate of Elsevier Inc.
6
Preprocessing
Preprocessing takes place in the computer where the algorithms determine the image histogram. Postprocessing is done by the technologist through various user functions. Digital preprocessing methods are vendor-specific.
Describe formation of an image histogram. Discuss automatic rescaling. Compare image latitude in digital imaging with film/screen radiography. List the functions of contrast enhancement parameters. State the Nyquist theorem.
Elsevier items and derived items © 2008 by Mosby, Inc., an affiliate of Elsevier Inc.
13
CR Image Sampling
For example:
• •
•
Pixels have a value of 1, 2, 3, and 4 for a specific exposure. Histogram shows the frequency of each of those values and actual number of values. Histogram sets the minimum (S1) and maximum (S2) “useful” pixel values.
制药工程专业英语课文翻译
Unit 1 Production of DrugsDepending on their production or origin pharmaceutical agents can be split into threegroups: I .Totally synthetic materials synthetics,Ⅱ.Natural products,and Ⅲ.Products from partial syntheses semi-synthetic products.The emphasis of the present book is on the most important compounds of groups I andⅢ一thus Drug synthesis. This does not mean,however,that natural products or otheragents are less important. They can serve as valuable lead structures,and they arefrequently needed as starting materials or as intermediates for important syntheticproducts.Table 1 gives an overview of the different methods for obtaining pharmaceuticalagents.1 单元生产的药品其生产或出身不同药剂可以分为三类:1。
完全(合成纤维)合成材料,Ⅱ。
天然产物,和Ⅲ。
产品从(半合成产品)的部分合成。
本书的重点是团体的最重要的化合物Ⅰ和Ⅲ一所以药物合成。
这并不意味着,但是,天然产品或其他代理人并不太重要。
它们可以作为有价值的领导结构,他们常常为原料,或作为重要的合成中间体产品的需要。
2024年高中生物会考题目及解答英文版
2024年高中生物会考题目及解答英文版2024 High School Biology Exam Questions and Answers1. What is the function of the mitochondria in a cell?- Answer: The mitochondria are known as the powerhouse of the cell, responsible for producing ATP through cellular respiration.2. Describe the process of photosynthesis.- Answer: Photosynthesis is the process by which plants use sunlight, carbon dioxide, and water to produce glucose and oxygen.3. What is the difference between mitosis and meiosis?- Answer: Mitosis is a type of cell division that results in two identical daughter cells, while meiosis is a form of cell division that produces four genetically different daughter cells.4. Explain the role of enzymes in biological reactions.- Answer: Enzymes act as catalysts in biological reactions, speeding up the rate of chemical reactions without being consumed in the process.5. How does the circulatory system function in the human body?- Answer: The circulatory system is responsible for transporting oxygen, nutrients, and waste products throughout the body using the heart, blood vessels, and blood.6. Discuss the importance of biodiversity in ecosystems.- Answer: Biodiversity is crucial for maintaining the balance of ecosystems, as it increases the resilience of the environment and provides various ecological services.7. What are the main differences between DNA and RNA?- Answer: DNA is a double-stranded molecule that stores genetic information, while RNA is a single-stranded molecule that helps in protein synthesis.8. Describe the process of protein synthesis.- Answer: Protein synthesis involves the transcription of DNA into mRNA, which is then translated into a specific sequence of amino acids to form proteins.9. Explain how natural selection leads to evolution.- Answer: Natural selection is the process by which organisms with advantageous traits are more likely to survive and reproduce, leading to changes in the genetic makeup of a population over time.10. What is the role of the immune system in the human body?- Answer: The immune system protects the body from pathogens and foreign invaders by recognizing and destroying them through a complex network of cells and proteins.This document provides a brief overview of the 2024 High School Biology exam questions and answers, covering various topics in the field of biology.。
光谱法研究药物小分子与蛋白质大分子的相互作用的英文
Spectroscopic Study of the Interaction between Small Molecules and Large Proteins1. IntroductionThe study of drug-protein interactions is of great importance in drug discovery and development. Understanding how small molecules interact with proteins at the molecular level is crucial for the design of new and more effective drugs. Spectroscopic techniques have proven to be valuable tools in the investigation of these interactions, providing det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding.2. Spectroscopic Techniques2.1. Fluorescence SpectroscopyFluorescence spectroscopy is widely used in the study of drug-protein interactions due to its high sensitivity and selectivity. By monitoring the changes in the fluorescence emission of either the drug or the protein upon binding, valuable information about the binding affinity and the binding site can be obt本人ned. Additionally, fluorescence quenching studies can provide insights into the proximity and accessibility of specific amino acid residues in the protein's binding site.2.2. UV-Visible SpectroscopyUV-Visible spectroscopy is another powerful tool for the investigation of drug-protein interactions. This technique can be used to monitor changes in the absorption spectra of either the drug or the protein upon binding, providing information about the binding affinity and the stoichiometry of the interaction. Moreover, UV-Visible spectroscopy can be used to study the conformational changes that occur in the protein upon binding to the drug.2.3. Circular Dichroism SpectroscopyCircular dichroism spectroscopy is widely used to investigate the secondary structure of proteins and to monitor conformational changes upon ligand binding. By analyzing the changes in the CD spectra of the protein in the presence of the drug, valuable information about the structural changes induced by the binding can be obt本人ned.2.4. Nuclear Magnetic Resonance SpectroscopyNMR spectroscopy is a powerful technique for the investigation of drug-protein interactions at the atomic level. By analyzing the chemical shifts and the NOE signals of the protein in thepresence of the drug, det本人led information about the binding site and the mode of binding can be obt本人ned. Additionally, NMR can provide insights into the dynamics of the protein upon binding to the drug.3. Applications3.1. Drug DiscoverySpectroscopic studies of drug-protein interactions play a crucial role in drug discovery, providing valuable information about the binding affinity, selectivity, and mode of action of potential drug candidates. By understanding how small molecules interact with their target proteins, researchers can design more potent and specific drugs with fewer side effects.3.2. Protein EngineeringSpectroscopic techniques can also be used to study the effects of mutations and modifications on the binding affinity and specificity of proteins. By analyzing the binding of small molecules to wild-type and mutant proteins, valuable insights into the structure-function relationship of proteins can be obt本人ned.3.3. Biophysical StudiesSpectroscopic studies of drug-protein interactions are also valuable for the characterization of protein-ligandplexes, providing insights into the thermodynamics and kinetics of the binding process. Additionally, these studies can be used to investigate the effects of environmental factors, such as pH, temperature, and ionic strength, on the stability and binding affinity of theplexes.4. Challenges and Future DirectionsWhile spectroscopic techniques have greatly contributed to our understanding of drug-protein interactions, there are still challenges that need to be addressed. For instance, the study of membrane proteins and protein-protein interactions using spectroscopic techniques rem本人ns challenging due to theplexity and heterogeneity of these systems. Additionally, the development of new spectroscopic methods and the integration of spectroscopy with other biophysical andputational approaches will further advance our understanding of drug-protein interactions.In conclusion, spectroscopic studies of drug-protein interactions have greatly contributed to our understanding of how small molecules interact with proteins at the molecular level. Byproviding det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding, spectroscopic techniques have be valuable tools in drug discovery, protein engineering, and biophysical studies. As technology continues to advance, spectroscopy will play an increasingly important role in the study of drug-protein interactions, leading to the development of more effective and targeted therapeutics.。
BinomialLinkFunctions:二项链接功能
following table:
Example (continued)
> beetle<-read.table("BeetleData.txt",header=TRUE)
> head(beetle)
Dose Num.Beetles Num.Killed
(Intercept) -34.935
2.648 -13.19 <2e-16 ***
Dose
19.728
1.487 13.27 <2e-16 ***
--Signif. codes: 0 ‘***’ 0.001 ‘**’ 0.01 ‘*’ 0.05 ‘.’ 0.1 ‘ ’ 1
(Dispersion parameter for binomial family taken to be 1)
yi
i 1
n
e
xi T ˆ
• Logit:
pˆ i
• Probit:
pˆ i ( xiT ˆ )
• C Log Log:
pˆ i 1 exp{ exp[ xiT ˆ ]}
1 e
xi T ˆ
Differences in Link Functions
probLowerlogit <- vector(length=1000)
family = binomial) > summary(logitmodel)
> probitmodel<-glm(cbind(Num.Killed,Num.Beetles-Num.Killed) ~ Dose, data = beetle,
英语英语英语英语
Shows the relative wavelengths of the electromagnetic waves of three different colors of light (blue, green and red) with a distance scale in micrometres along the x-axis.
Since light is an oscillation it is not affected by travelling through static electric or magnetic fields in a linear medium such as a vacuum. However in nonlinear media, such as some crystals, interactions can occur between light and static electric and magnetic fields — these interactions include the Faraday effect and the Kerr effect.
Electromagnetic radiation is classified according to the frequency of its wave. In order of increasing frequency and decreasing wavelength, these are radio waves, microwaves, infrared radiation, visible light, ultraviolet radiation, X-rays and gamma rays (see Electromagnetic spectrum). The eyes of various organisms sense a small and somewhat variable window of frequencies called the visible spectrum. The photon is the quantum of the electromagnetic interaction and the basic "unit" of light and all other forms of electromagnetic radiation and is also the force carrier for the electromagnetic force.
药代动力学英文实验步骤
药代动力学英文实验步骤1. Study Design: Determine the study design, including the route of administration (oral, intravenous, etc.), dose, and sampling schedule.2. Animal Preparation: Prepare the experimental animals, ensuring they meet the specified requirements for the study.3. Administration of the Drug: Administer the test drug to the animals according to the study design.4. Blood Sampling: Collect blood samples at specified time points after drug administration. The sampling schedule may vary depending on the study aims.5. Plasma Preparation: Prepare plasma samples by centrifugation of the blood samples to separate the plasma from the blood cells.6. Analytical Method Development: Establish a reliable analytical method for quantification of the drug in the plasma samples. This may include HPLC, LC-MS/MS, or other appropriate techniques.7. Method Validation: Validate the analytical method to ensure accuracy, precision, linearity, and specificity.8. Sample Analysis: Analyze the plasma samples using the validated analytical method to determine the drug concentration at each time point.9. Data Analysis: Calculate the pharmacokinetic parameters, such as AUC, Cmax, Tmax, half-life, clearance, and volume of distribution, using appropriate pharmacokinetic software.10. Interpretation of Results: Interpret the pharmacokinetic data, comparing it with literature values or预期结果. Evaluate the absorption, distribution, metabolism, and elimination of the drug.11. Reporting: Prepare a report summarizing the study design, methodology, results, and conclusions.It's important to note that the specific steps and details may vary depending on the nature of the drug, the study objectives, and the regulatory requirements.Additionally, adhering to ethical guidelines and following Good Laboratory Practice (GLP) or equivalent standards is essential throughout the experimental process. If you have specific questions or need more detailed information, please provide the specific drug and study context, and I will do my best to assist you further.。
山东大学博士开题报告.pdf
Short-distance and long-distance are separately gauge invariant.
Do Not Delete This.
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Factorization
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Motivation
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Factorization
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Ward identities
H(n)→H(n-1)
gauge link (A+)
Wei Shuyi @ sdu
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Spin Dependence
Hadronic Tensor = Hard × Gauge Invariant Matrix (4×4)
Gamma Matrices × Lorentz Covariants
Calculate with Models Light-cone wave function, String, Cluster
Di-hadron correlation….
Thanks for your attention!
2012-11-20
Wei Shuyi @ sdu
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Backup
Subsection
ImportanceofthePre-RequisiteSubject
Importance of the Pre-Requisite SubjectK.Kadirgama, M.M.Noor, M.R.M.Rejab, A.N.M.Rose, N.M. Zuki N.M., M.S.M.Sani, A.Sulaiman,R.A.Bakar, Abdullah IbrahimUniversiti Malaysia Pahang,***************.myABSTRACTIn this paper, it describes how the pre-requisite subjects influence the student’s performance in Heat transfer subject in University Malaysia Pahang (UMP). The Pre-requisite for Heat transfer in UMP are Thermodynamics I and Thermodynamics II. Randomly 30 mechanical engineering students were picked to analysis their performance from Thermodynamics I to Heat transfer. Regression analysis and Neural Network were used to prove the effect of prerequisite subject toward Heat transfer. The analysis shows that Thermodynamics I highly affect the performance of Heat transfer. The results show that the students who excellent in Thermodynamics I, their performance in Thermodynamics II also the same and goes to Heat transfer. Those students who scored badly in their Thermodynamics I, the results for the Thermodynamics II and Heat transfer are similar to Thermodynamics I. This shows the foundation must be solid, if the students want to do better in Heat transfer.INTRODUCTIONPre-requisite means course required as preparation for entry into a more advanced academic course or program [1]. Regression analysis is a technique used for the modeling and analysis of numerical data consisting of values of a dependent variable (response variable) and of one or more independent variables (explanatory variables). The dependent variable in the regression equation is modelled as a function of the independent variables, corresponding parameters ("constants"), and an error term. The error term is treated as a random variable. It represents unexplained variation in the dependent variable. The parameters are estimated so as to give a "best fit" of the data. Most commonly the best fit is evaluated by using the least squares method, but other criteria have also been used [1].Regression can be used for prediction (including forecasting of time-series data), inference, hypothesis testing, and modelling of causal relationships. These uses of regression rely heavily on the underlying assumptions being satisfied. Regression analysis has been criticized as being misused for these purposes in many cases where the appropriate assumptions cannot be verified to hold [1, 2]. One factor contributing to the misuse of regression is that it can take considerably more skill to critique a model than to fit a model [3].However, when a sample consists of various groups of individuals such as males and females, or different intervention groups, regression analysis can be performed to examine whether the effects of independent variables on a dependent variable differ across groups, either in terms of intercept or slope. These groups can be considered from different populations (e.g., male population or female population), and the population is considered heterogeneous in that these subpopulations may require different population parameters to adequately capture their characteristics. Since this source of population heterogeneity is based on observed group memberships such as gender, the data can be analyzed using regression models by taking into consideration multiple groups. In the methodology literature, subpopulations that can be identified beforehand are called groups [4, 5].Model can account for all kinds of individual differences. Regression mixture models described here are a part of a general framework of finite mixture models [6] and can be viewed as a combination of the conventional regression model and the classic latent class model [7, 8]. It should be noted that there are various types of regression mixture models [7], but this only focus on the linear regression mixture model. Thefollowing sections will first describe some unique characteristics of the linear regression mixture model in comparison to the conventional linear regression model, including integration of covariates into the model. Second, a step-by-step regression mixture analysis of empirical data demonstrates how the linear regression mixture model may be used by incorporating population heterogeneity into the model.Ko et al. [9] have introduced an unsupervised, self-organised neural network combined with an adaptive time-series AR modelling algorithm to monitor tool breakage in milling operations. The machining parameters and average peak force have been used to build the AR model and neural network. Lee and Lee [10] have used a neural network-based approach to show that by using the force ratio, flank wear can be predicted within 8% to 11.9% error and by using force increment, the prediction error can be kept within 10.3% of the actual wear. Choudhury et al. [11] have used an optical fiber to sense the dimensional changes of the work-piece and correlated it to the tool wear using a neural network approach. Dimla and Lister [12] have acquired the data of cutting force, vibration and measured wear during turning and a neural network has been trained to distinguish the tool state.This paper will describe the influence of prerequisite subject toward Heat transfer. The analysis will be done using regression method and Neural Network.REGRESSION METHODIn linear regression, the model specification is that the dependent variable, yi is a linear combination of the parameters (but need not be linear in the independent variables). For example, in simple linear regression for modelling N data points there is one independent variable: xi, and two parameters, β0 and β1 [2]:Results from the 30 mechanical engineering students were collected. There are mixed between female and male, no age different, different of background and all the students from same class. Regression analysis was done to check the most dominant variables (Thermodynamics I and Thermodynamics II) effect towards response (Heat transfer). Table 1 shows the marks of the students.Table 1: Marks for the subjects.Student Thermodynamics1 Thermodynamics2Heat transfer1 85 83 852 51 50 533 67 65 694 55 61 555 44 51 516 64 63 557 42 50 498 54 63 609 58 50 5810 52 61 6011 69 77 7712 58 64 6813 57 61 6814 71 68 6015 61 70 7316 53 66 6217 60 71 5918 45 55 5719 47 60 5620 62 77 6921 45 60 53(1)22 40 52 3723 53 70 6224 53 61 7025 56 60 7326 51 63 6927 44 62 5728 40 58 5229 62 80 7130 47 63 46MULTILAYER PERCEPTIONS NEURAL NETWORKIn the current application, the objective is to use the supervised network with multilayer perceptrons and train with the back-propagation algorithm (with momentum). The components of the input pattern consist of the control variables used in the student performance (Thermodynamics I and Thermodynamics II), whereas the components of the output pattern represent the responses from sensors (Heat transfer). During the training process, initially all patterns in the training set were presented to the network and the corresponding error parameter (sum of squared errors over the neurons in the output layer) was found for each of them. Then the pattern with the maximum error was found which was used for changing the synaptic weights. Once the weights were changed, all the training patterns were again fed to the network and the pattern with the maximum error was then found. This process was continued till the maximum error in the training set became less than the allowable error specified by the user. This method has the advantage of avoiding a large number of computations, as only the pattern with the maximum error was used for changing the weights. Fig.1 shows the neural network computational mode with 2-5-1 structure.Fig. 1: Neural Network with 2-5-1 structure. Heat transferThermodynamic IIRESULTS AND DISCUSSIONThe regression equation as below:Heat transfer = 8.04 + 0.498 Thermodynamics I + 0.408 Thermodynamics II (2)Equation 2 shows that Thermodynamics I is more dominant compare with Thermodynamics II. One can notice that, increase in Thermodynamics I and Thermodynamics II it will increase the result in Heat transfer. Table 2 show that Thermodynamics really significantly effect the heat transfer. It means, those have a very good foundation in Thermodynamics I, they can do better in Heat transfer. The p-value in the Analysis of Variance Table 2 (0.000) indicates that the relationship between Thermodynamics I and Thermodynamics II is statistically significant at an a-level of 0.05. This is also shown by the p-value for the estimated coefficient of Thermodynamics I, which is 0.008 as shown in Table 3.Table 2: Analysis of VarianceFPSSMSSource DF22.64936.93Regression 2 1873.87Residual Error 27 1117.6 41.39Total 29 2991.47Table 3: Estimated coefficientTCoefPSEPredictor Coef0.920.3678.771Constant 8.043Thermodynamics1 0.498 0.1734 2.870.008Thermodynamics2 0.4079 0.2032 2.01 0.055Fig. 2 shows the sensitivity test. The test shows that Thermodynamics I is the main effect for the heat transfer. The results for the sensitivity test and regression analysis show the same results.Fig.2: Sensitivity TestCONCLUSIONThe regression analysis and Neural Network is very useful tool to do analysis in term of measure student performance and importance of prerequisite subject. The results prove that Thermodynamics I effect lot the student performance in Heat transfer. The foundation subject must be very strong, if the students want to perform better in Thermodynamics II and Heat transfer. ACKNOWLEDGEMENTThe authors would like to express their deep gratitude to Universiti Malaysia Pahang (UMP) for provided the financial support.REFERENCESRichard A. Berk, Regression Analysis: A Constructive Critique, Sage Publications (2004)David A. Freedman, Statistical Models: Theory and Practice, Cambridge University Press (2005)R. Dennis Cook; Sanford Weisberg "Criticism and Influence Analysis in Regression", Sociological Methodology, Vol. 13. (1982), pp. 313-361.Lubke, G. H., & Muthén, B. (2005). Investigating population heterogeneity with factor mixture models. Psychological Methods, 10(1), 21-39.Muthen, B. O., & Muthen, L. K. (2000). Integrating person-centered and variable-centered analyses: Growth mixture modeling with latent trajectory classes. Alcoholism: Clinical and Experimental Research, 24, 882-891.Nagin, D., & Tremblay, R. E. (2001). Analyzing developmental trajectories of distinct but related behaviors: A group-based method. Psychological Methods, 6, 18-34.Lazarsfeld, P. F., & Henry, N. W. (1968). Latent structure analysis. Boston: Houghton Mifflin Company.McCutcheon, A. L. (1987). Latent class analysis. Thousand Oaks, CA: Sage Publications, Inc.T. J .Ko, D. W Cho, M. Y. Jung,” On-line Monitoring of Tool Breakage in Face Milling: Using a Self-Organized Neural Network”, Journal of Manufacturing systems, 14(1998), pp. 80-90.J.H. Lee, S.J. Lee,” One step ahead prediction of flank wear using cutting force”, Int. J. Mach. Tools Manufact, 39 (1999), pp 1747–1760.S.K. Chaudhury, V.K. Jain, C.V.V. Rama Rao,” On-line monitoring of tool wear in turning using a neural network”; Int. J. Mach. Tools Manufact, 39 (1999), pp 489–504.D.E. Dimla, P.M. Lister,” On-line metal cutting tool condition monitoring. II: tool state classification using multi-layer perceptron neural network”, Int. J. Mach. Tools Manufact ,40 (2000), pp 769–781。
二次量子化英文文献
二次量子化英文文献An Introduction to Second Quantization in Quantum Mechanics.Abstract: This article delves into the concept of second quantization, a fundamental tool in quantum field theory and many-body physics. We discuss its historical development, mathematical formalism, and applications in modern physics.1. Introduction.Quantum mechanics, since its inception in the early20th century, has revolutionized our understanding of matter and energy at the atomic and subatomic scales. One of the key concepts in quantum theory is quantization, the process of assigning discrete values to physical observables such as energy and momentum. While first quantization focuses on the quantization of individual particles, second quantization extends this principle tosystems of particles, allowing for a more comprehensive description of quantum phenomena.2. Historical Development.The concept of second quantization emerged in the late 1920s and early 1930s, primarily through the works of Paul Dirac, Werner Heisenberg, and others. It was a natural extension of the first quantization formalism, which had been successful in explaining the behavior of individual atoms and molecules. Second quantization provided a unified framework for describing both bosons and fermions, two distinct types of particles that exhibit different quantum statistical behaviors.3. Mathematical Formalism.In second quantization, particles are treated as excitations of an underlying quantum field. This approach introduces a new set of mathematical objects called field operators, which act on a Fock space – a generalization of the Hilbert space used in first quantization. Fock spaceaccounts for the possibility of having multiple particles in the same quantum state.The field operators, such as the creation and annihilation operators, allow us to represent particle creation and destruction processes quantum mechanically. These operators satisfy certain commutation or anticommutation relations depending on whether the particles are bosons or fermions.4. Applications of Second Quantization.Second quantization is particularly useful in studying systems with many particles, such as solids, gases, and quantum fields. It provides a convenient way to describe interactions between particles and the emergence of collective phenomena like superconductivity and superfluidity.In quantum field theory, second quantization serves as the starting point for perturbative expansions, allowing physicists to calculate the probabilities of particleinteractions and scattering processes. The theory has also found applications in particle physics, cosmology, and condensed matter physics.5. Conclusion.Second quantization represents a significant milestone in the development of quantum theory. It not only extends the principles of quantization to systems of particles but also provides a unified mathematical framework for describing a wide range of quantum phenomena. The impact of second quantization on modern physics is profound, and its applications continue to expand as we delve deeper into the quantum realm.This article has provided an overview of second quantization, its historical development, mathematical formalism, and applications in modern physics. The readeris encouraged to explore further the rich and fascinating world of quantum mechanics and quantum field theory.。
Flow patterns and draining films created by inclined coherent water jets impinging on vertical walls
Flow patterns and draining films created by horizontal and inclined coherent water jets impinging on vertical wallsT.Wang,D.Faria,L.J.Stevens,J.S.C.Tan,J.F.Davidson,D.I.Wilson nDepartment of Chemical Engineering &Biotechnology,University of Cambridge,New Museums Site,Pembroke Street,Cambridge CB23RA,UKH I G H L I G H T SFlow patterns created by liquid jets impinging at angles off horizontal are studied. Little effect of gravity and contact angle at flow rates studied.Width and height of radial impingement region are predicted by the model. Falling film width is correlated with film jump radius.Formation of dry patches in falling film is predicted by the model.a r t i c l e i n f oArticle history:Received 1June 2013Received in revised form 11August 2013Accepted 24August 2013Available online 4September 2013Keywords:CleaningContact angle Fluid flow Impinging jet Surface tensiona b s t r a c tThe flow patterns created by coherent water jets created by solid stream nozzles impinging on vertical polymethylmethacrylate (Perspex)and glass surfaces were studied for nozzles with diameters 2–4mm at angles up to 7451from the horizontal.The flow rates studied ranged from 7.1to 133g s À1(26–480L h À1;jet velocities 2.6–10.6m s À1).The width and height of the film jump marking the limit of the radial flow zone were compared with models based on that developed by Wilson et al.(2011),modi fied to include the effect of gravity and the angle of inclination for non-horizontal jets (incorporat-ing the flow distribution model reported by Kate et al.(2007.Journal of Fluid Mechanics 573,247–263)).The location of the film jump and the flow pattern around the impingement point were sensitive to the nature of the substrate at low flow rates,but insensitive to substrate nature at higher flow rates.The models predicted the film jump location with reasonable accuracy,and the width of the wetted region at the mid-plane was found to follow a simple relationship to the film jump width there.A first-order model for the width of the rope of liquid draining around the film jump gave a lower bound estimate of this dimension.The falling film generated below the impingement point exhibited three forms of behaviour:a wide film,termed gravity flow ;a narrowing film,termed rivulet flow ,and a wide film which split into two with the formation of a dry patch .The transition to form a dry patch was found to obey the minimum wetting rate criterion reported by Hartley and Murgatroyd (1964),once loss of liquid due to splashback was accounted for.Dry patch formation within the falling film was only observed with upwardly impinging jets,and the tendency to form dry patches was predicted with some success by a simple two-stream model.&2013Elsevier Ltd.All rights reserved.1.IntroductionLiquid jets are widely used to remove surface soiling (fouling)layers when cleaning process equipment (Jensen,2011).Their use for cleaning the internals of tanks and other vessels is increasing as they offer several advantages over simple ‘fill and soak ’strategies in employing smaller volumes of liquid.Mechanical energy is required for pumping but this is usefully dissipated bythe liquid,usually water-based,as it flows over the soil:the flow imposes a shear stress which enhances soil break-down and increases convective heat transfer as well as mass transfer of soluble species into the liquid.The performance of jet cleaning systems such as spray balls,solid-stream nozzles,jet heads and rotating spray arms (e.g .in dishwashers)depends strongly on the wetting patterns of the liquid on the wall.For cases where cleaning arises primarily from the chemical or detergent action of the liquid,it is important to be able to predict whether the design will achieve complete coverage of the target area with liquid.For cases where cleaning also requires a high shear stress,knowledge of the shear stressContents lists available at ScienceDirectjournal homepage:/locate/cesChemical Engineering Science0009-2509/$-see front matter &2013Elsevier Ltd.All rights reserved./10.1016/j.ces.2013.08.054nCorresponding author.Tel.:þ441223334791.E-mail address:diw11@ (D.I.Wilson).Chemical Engineering Science 102(2013)585–601distribution is required.Both instances require a working knowl-edge of theflow patterns created by the liquid jet.This paper investigates theflow patterns created by coherent liquid jets impinging on vertical surfaces,such as are created by solid stream nozzles and by spray balls before the jet breaks up(caused by Rayleigh instabilities).Studies of spray jets in cleaning have been presented by Leu et al.(1998)and Meng et al.(1998).Theflow patterns generated by coherent liquid jets impinging vertically downwards on horizontal surfaces,giving circular regions of rapid,radialflow terminating with an abrupt change infilm height called the hydraulic jump,have been studied for over50years.The phenomenology,including the formation of surface waves and influence of surface tension,has been estab-lished and modelled by successive workers(e.g.Watson,1964; Bush and Aristoff,2003).The case of a non-vertical jet impinging on a horizontal plate and forming a non-circular hydraulic jump has been modelled by Blyth and Pozrikidis(2005),Kibar et al. (2010)and by Kate et al.(2007).Button et al.(2010)reported an elegant study and model of the less common case,where a liquid jetflowing vertically upwards impinges on a horizontal plate, spreads radially outwards and falls downwards to form a‘water bell’.The behaviour of jets impinging on vertical or near-vertical surfaces has received less attention despite its importance in cleaning.Morison and Thorpe(2002)reported a study of the contact region,drainingfilm and cleaning behaviour generated by individual spray ball jets operating at industrialflow rates.They studied jets created by spray ball holes with diameters1.6–2.4mm at pressures up to 3.6barg at velocities ranging from7to 28m sÀ1.Atomisation was not observed in their tests.On a vertical wall,the liquidflows radially outwards from the point of impingement until a feature resembling a hydraulic jump occurs, which is here termed thefilm jump.Knowledge of the location of thefilm jump is important as this is the boundary of the radialflow zone(RFZ)where the highest shear stresses are generated.Wilson et al.(2011)analysed Morison and Thorpe's data sets as well as new experimental data and showed that the size of the RFZ could be predicted by a simplified model derived from the work by Button et al.;in this simplified model thefilm jump occurs when the radially outwardflow of momentum is balanced by surface tension at radial location R(see Fig.1),given byR¼0:276_m3μργð1ÀcosβÞ"#1=4ð1Þwhere_m is the massflow rate,μis the liquid kinematic viscosity,ρits density,γis the gas–liquid surface tension andβthe contact angle.Beyond thefilm jump theflow pattern is complex.Fig.1shows schematics of three types of behaviour observed in this work.The pattern above the plane of impingement is common to all,where beyond thefilm jump the liquid falls circumferentially in a rope until it reaches the plane of impingement,beyond which it falls downwards.The width of the rope and RFZ at the impingement plane(labelled X–X)is2R c.An a priori prediction for R c is currently not available.Wilson et al.(2011)and Wang et al.(2013)observed that R c E2R at lowerflow rates and approached R c E4R/3at higherflow rates(above11g sÀ1for a3mm nozzle).Theflow rate at which the transition in R c/R behaviour occurred depended on the substrate and thus the contact angle.In the case where downward momentum dominates surface tension(Fig.1(a)),theflow forms a stable fallingfilm of width W, which is here termed gravityflow.Thefilm width may change gradually.In cases where surface tension is significant,two behaviours can arise:rivuletflow,Fig.1(b),where the liquid forms a narrow tail,and dry patch formation,Fig.1(c),where the falling film splits.Both rivuletflow and dry patch formation are undesir-able for cleaning applications.Wilson et al.studied waterflow rates which were low com-pared to those used in industrial cleaning jets,up to2.0g sÀ1,and observed either gravity or rivuletflow.They found that the occurrence of stable widefilms,of width W,could be predicted by the criterion for the minimum wetting rate,Γmin,for stable fallingfilms developed for evaporators by Hartley and Murgatroyd (1964)viz.Γ¼_m=W Z1:69ðμρ=gÞ0:2½γð1ÀcosβÞ 0:6¼Γminð2Þwhere g is the gravitational acceleration.The reliability of this criterion for higherflow rates is explored here.Wang et al.(2013)studied the effect of a surfactant,Tween20, for similarflow rates and found the presence of surfactant to have little influence on the size of thefilm jump,but strongly affected fallingfilm behaviour.This was attributed to dynamic contact angle effects:in the fallingfilm there was sufficient time for the surfactant to accumulate at the wetting line and influence the contact angle.The contact angle is also determined by the nature of the substrate.Wang et al.(2013)reported results for jets impinging on vertical glass and Perspex(polymethylmethacrylate)substrates, which have different water contact angles.At lowerflow rates (o11g sÀ1at201C),the location of thefilm jump was sensitive to substrate nature but at higherflow rates,obtained by Wang et al. using larger nozzles,thefilm jump location was insensitive to substrate nature.Drainingfilm behaviour continued to be sensitive to the substrate and static contact angle.XFig.1.Schematics offlow patterns,viewed from behind target in Fig.2,generated by a jet impinging on a vertical plate.O is the jet impingement point,R is the radius of the film jump,R c is the radius of the corona or rope at the impingement level(X–X).Z r is the height of inner radial zone above O;Z t is the maximum height of thefilm above O. The grey arrows show theflow pattern:radial from O to the jump;tangential around the rim.The polar coordinate isθ.Flow regimes below X–X are(a)Gravityflow,with a drainingfilm of width W at z,where z is the distance measured downwards from O.(b)Rivuletflow.(c)Gravityflow,with dry patch formation.T.Wang et al./Chemical Engineering Science102(2013)585–601586This paper reports an investigation of coherent water jets impinging on vertical walls at higher flow rates than those reported by Wilson et al.and Wang et al.The flow rates employed are at the low end of those used in industrial cleaning nozzle devices 1and establish some of the fundamental aspects of the flows in these devices.Wilson et al.'s model is modi fied to include gravitational effects as well as the case where the jet impinges at an oblique angle,i.e .the jet is not horizontal.2.Materials and methodsTwo apparatuses were used in this work.The majority of the results reported here were generated using the system in Fig.2,which consisted of a 1.2m Â1.2m Â1.7m high chamber with Perspex walls containing a vertical nozzle locating rail and a vertical target.The test liquid was tap water at room temperature.Cambridge water is hard (315ppm as calcium carbonate)and its surface tension was measured at 74.671mN m À1(Wilson et al.,2011).Water was pumped from a 26L holding tank through one of two rotameters,thereby covering the range of mass flow rates in the range 7–133g s À1(400–8000mL min À1).A flexible hoseallowed the elevation and angle of the nozzle on the locating rail to be adjusted as desired.The nozzles were fabricated from cylindrical brass blanks 9mm in diameter,and 30mm in length (see Fig.3).The dimensions of the nozzles are summarised in Table 1.The ori fice sizes,d N ,(i.d.2,3and 4mm)were selected to lie in the range of commercial cleaning-in-place (CIP)nozzles.The nozzle was connected to the entry pipe of inner diameter 7.5mm with a 150mm long straigh-tening section.The liquid jet from the nozzle impinged on the vertical target surface at a horizontal distance l away from the nozzle.For the tests reported here,l was approximately 50mm and the Reynolds number in the pipe upstream of the nozzle,Re pipe ,ranged from 1450to 10,800,while those in the nozzle throat,Re jet ,varied from 4300to 20,300.Re jet is calculated from Re jet ¼U o r o =ν,where U o and r o are the jet velocity and radius,respectively,and νis the liquid dynamic viscosity.Also shown in Table 1are the values of the coef ficient of velocity,C v ,for each nozzle.C v is de fined as the ratio of the actual velocity to the theoretical velocity calculated assuming plug flow across the nozzle cross-section.The actual velocity was deter-mined by a simple measurement of how high a vertical jet rose in air before gravity caused it to stop rising and cascade downwards.The results show that for d N ¼3mm and 4mm,covering the majority of tests reported here,C v ¼1and thus r o ¼d N /2.The target was a vertical plate of float glass (height 1000mm,width 800mm)mounted on an aluminium alloy frame.Water impinged on one side and the resulting flow pattern was photo-graphed using a Nikon 12megapixel camera located behind the target as shown in Fig.2.Transparent ruled tape was attached to the dry side of the target to allow distances to be read off photographs reliably.The width of the falling film at a given point,W ,was measured horizontally.The wetting rate at that point,Γ,was calculated from Γ¼_m=W .A separate Perspex plate could be attached to the frame.The advancing contact angle of the tap water on the glass was measured using a Kruss DSA 100S drop shape analyser as 39751;the value on Perspex was 72.5751.Surface roughness,R a ,was measured using a pro filometer.This gave R a for the glass of 0.008μm and that of the Perspex $0.02μm.At high flow rates there was noticeable splattering where liquid splashed back off the surface following impact.Splattering does not affect the velocity of the liquid in the radial flow zone,but it reduces the flow rate in the falling film and thus the wetting rate.The amount of splattering was measured by weighing the liquid which accumulated in the collection tray (Fig.2)over a set time and comparing this with the nozzle feed rate.The nozzle feed rate was measured separately by a catch and weigh method.The fraction splattered,ξ,was evaluated from ξ¼1À_mðcollected Þ_ð3ÞThe results in Fig.4show that there was little noticeable splatter-ing until Re jet reached 12,000for all three nozzles tested.Thenegative values on the plot at low Re jet values result from the uncertainty in the method for collecting the flow.At higher velocities ξincreased almost linearly with Re jet ,independentofFig.2.Schematic diagram of the apparatus for jet impinging onto a verticalsurface.Fig.3.Nozzle cross-section.Table 1Nozzle dimensions (see Fig.3)and flow parameters.Nozzle diameter,d N (mm)Internal diameter d i (mm)Inlet length,L i (mm)Throat length,L t (mm)Re pipeRe jetC v29 2.50.7580–57802170–17,1000.839 2.60.6580–79401440–19,8001492.40.82890–10,8005300–20,30011For example,a typical industrial 4mm diameter rotary jet cleaning head operating at 5barg would deliver water at a flow rate of 400g s À1.T.Wang et al./Chemical Engineering Science 102(2013)585–601587nozzle diameter.However,Fig.4(b)shows that the amount of splash back increased signi ficantly for upwardly inclined jets,with the largest amount of splash back at the greatest upward impinge-ment angle.The data were also compared with the models for splattering reported by Bhunia and Lienhard (1994)and Lienhard et al.(1992)for jets generated by flow through a long capillary striking a rigid flat surface.Those models did not give reliable predictions of the amount of splattering observed here,which is attributed to the use of convergent nozzles and a relatively short pipe entry length in this work.3.Model developmentTheoretical developments are presented in two sections.Section 1outlines models for predicting the size of the radial flow zone in the presence of gravity,the rope width,and the effect of jet inclination.Section 2describes an approach for predicting the formation of dry patches in the falling liquid film resulting from an inclined jet.3.1.Effect of gravity on the radial flow region for a horizontal jet impinging on a vertical surfaceFig.5(a)shows a schematic of a horizontal liquid jet with radius r oand volumetric flow rate,Q ,striking a vertical surface atimpingement point O.The jet is in plug flow with velocity U o ,where Q ¼πr 2o U o .The liquid flows radially away from the point of impingement:at a distance r (4r o )the film thickness is h and the local mean velocity is U .Following the analysis presented by Wilson et al.(2011),a momentum balance on a streamline gives d dr ðMr Þ¼d dr 65ρhU 2r¼Àτr Àrh ρg cos θð4Þwhere M is the momentum flux per unit width,ρis the liquid density,τthe wall shear stress and θis the angle of inclination of the streamline to the vertically upwards direction (see Fig.1(a)).Surface tension does not appear in (4)as it does not create a resultant force.In the RFZ the liquid film is assumed to have a well-developed laminar velocity pro file.The distance required to develop this pro file is discussed by Watson (1964)and Yeckel and Middleman (1987).For a Newtonian fluid the wall shear stressisFig.4.Effect of jet Reynolds number on splattered fraction ξ;no splattering is indicated by the horizontal dashed line,ξ¼0.The distance from the nozzle to the target plate is l ¼50mm.for (a)horizontal jets,d N ¼2,3and 4mm;(b)Effect of jet inclination angle,ϕ,with d N ¼3mm.Solid symbols –downward jet,ϕo 901;open symbols,upward jet,ϕZ 901.Data in (b)provided by Atkinson and Suddaby (2013).ϕValues indegrees.Fig. 5.Schematic of (a)horizontal liquid jet impinging on a vertical surface,showing geometry of radial film (b)surface tension forces involved in termination of the radial film.T.Wang et al./Chemical Engineering Science 102(2013)585–601588given by (Nusselt,1916)τ¼3μU hð5ÞAssuming no loss due to splashback or spray formation,the local film thickness at r may be calculated from Q ¼2πhrUð6ÞCombining Eqs.(4)–(6)gives d dr QU 2π ¼À5πνU 2r 2Q À56Qg cos θ2πU ð7ÞSimplifyingd U ¼À10π2νU 2r 2Q À5g cos θð8ÞThe local velocity U at location r is obtained by integrating (8)subject to the boundary condition U ¼U o at r ¼r o .This analysis differs from that presented by Wilson et al.(simpli fied model)in the inclusion of the gravity term.The in fluence of gravity can be estimated by comparing the two terms on the right hand side.This implies that the deceleration of liquid moving vertically above thepoint of impingement is larger if gravity is included.The contribu-tion from gravity increases as U decreases,i.e .at large r .The flow stops spreading outwards at R when the radial momentum is matched by the force due to surface tension,shown in Fig.5(b).A force balance gives,as a boundary condition 6ρU 2Rh R ¼γð1Àcos βÞð9ÞSubstituting for h R using (6)with h ¼h R and r ¼R ,yields U R ¼5π3γð1Àcos βÞρQRð10ÞR is found by integrating (8)to give U (r )and finding the radial position which satis fies (10).This requires integration and is solved numerically to find R .The effect of θon R is compared with experimental observations in Section 4.2.At higher flow rates (such as shown later in Fig.15for _m¼50g s À1),the rope becomes less stable and the precise location of the termination of outward flow may be obscured by liquid from the rope falling down across the surface under the in fluence of gravity.This gravity model (Eqs.(8)–(10))indicates that the radial flow zone should be non-circular since the component of g acting in the direction of the streamline varies from –9.81m s À2to zero as the streamlines move from the vertical to the horizontal.This aspect was not considered by Wilson et al.(2011)in their study as their focus was on the width of the falling film generated by the impinging jet.The above analysis is not expected to apply to the flow below the impingement plane (labelled X –X in Fig.1)as gravity causes the flow to accelerate downwards and the boundary condition for the film jump is in fluenced by liquid draining from above.Eq.(9)does not include these effects.3.2.Flow in the ropeFig.6(a)describes a simple model for predicting the width of the rope region.The photograph in Fig.6(b)shows that the flow in this region is unstable:this model provides a first order descrip-tion of the phenomenon.The rope consists of liquid falling under gravity after its radial flow is terminated.The liquid descends,flowing around the edge of the film jump radius,r in ,while collecting more liquid from the radial flow.The rope width,r out Àr in ,increases from the crown down to the impingement plane.Below the latter the rope spreads out into the draining film.In this model,the radial flow zone is assumed to be circular and symmetrical.The values of r in and r out at θ¼01(i.e .the crown)are labelled Z r and Z t ,respectively,and are compared with experi-mental data in Fig.18(discussed later),while the corresponding values at θ¼901are labelled R and R c .Flow in the rope is assumed to increase uniformly with angle θup to 901.The rope width,D ,is small such that the average radius,r avg ¼1=2ðr in þr out Þ%r in .The cross section of the rope is assumed to be semi-circular,as shown in the inset in Fig.6(a),so that the width of the rope can be calculated from the cross sectional area,A .This shape assumption is unlikely to be accurate and the rope is expected to be wider than that calculated.The liquid flow is deemed to be proportional to the angular coordinate,θ,soAu ¼Q θ ¼Q θð11Þwhere u is the tangential velocity within the rope and θis inradians.A momentum balance on an element of rope,assuming negligible wall shear,then gives ρgAr in d θsin θ¼d ðρAu 2Þ¼ρQ2πd ðu θÞð12ÞFig. 6.(a)Schematic of the geometry and flow in the rope.Inset shows the assumed rope cross-section.(b)Photograph of the rope.Dashed line indicates location of the film jump.T.Wang et al./Chemical Engineering Science 102(2013)585–601589Combining(11)and(12),eliminating A,givesd dθðuθÞ22!¼gr inθ2sinθð13ÞIntegrating with the boundary condition uθ¼0atθ¼01gives the mean velocity as a function of the angular position,viz.u2 2gr in ¼2sinθθþ2ðcosθÀ1Þθ2Àcosθ¼f ropeðθÞð14ÞSubstituting u from(14)to(11)and assuming r in¼R gives an expression for A(θ)which can then be related to the width of the rope,D at that position,fromDðθÞ¼2ffiffiffiffiffiffiffiffiffiffiffiffiffiQffiffiffiffiffiffiffiffiffi2gRpsffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiθffiffiffiffiffiffiffiffiffiffiffiffiffiffiffif ropeðθÞqv uu tð15Þ3.3.Obliquely impinging jets(oblique jet model)The analysis is extended to non-horizontal jets impinging on a vertical surface,employing theflow distribution model presented by Kate et al.(2007)for jets impinging obliquely on a horizontal surface.The angle of impingement,α,is defined as positive if approaching the impingement point from above,see Fig.7(a).The geometry is simplified if the angle to the vertical,labelledϕ,is used,whereαþϕ¼π/2.The following paragraphs summarise the Kate et al.model.The circular jet forms an elliptical zone on impact,as shown in Fig.7(b).Kate et al.showed that in the initial impingement zone liquid moves radially outward from a source,labelled S,located a distance r o cotϕfrom the point of impingement,O.Applying Bernoulli's equation in this(small)impingement zone shortly after the start of thefilm implies that the mean velocity in thefilm is U o at the edge of the ellipse.Beyond this ellipse the liquidflows radially but loses energy against wall friction,as in model I.A.S lies at one of the foci of the ellipse,and the radial distance from S to the edge of the impingement zone where u¼U o,r e,at angleθto the major axis(as shown in thefigure)is given byr e r o ¼sinϕ1þcosϕcosθð16ÞKate et al.also showed that the height of thefilm,h p,at the radial distance of a point,r p,located on the plate,is given byh p¼r2esinϕ2r pð17ÞBeyond the edge of the ellipse,radialflow is assumed to continue. Applying continuity to the element offlow dQ along a streamline at angleθyieldsdQ¼U o h e r e dθ¼Uhrdθr Z r eð18ÞSubstituting(17)in(18)gives1 2U o r2esinϕ¼rhUð19ÞThe momentum balance on a streamline(Eq.(8))can then be written asdρU r 2eU o sinϕ¼À5μUr2rUo e À5ρg cosθU o r2esinϕð20ÞThis simplifies todU dr ¼À10νU2or4esin2ϕr2U2À56g cosθUð21Þwhich collapses to Eq.(8)forϕ¼π/2.This needs to be integratednumerically,as in I.A.,if gravity is considered.Gravity is ignored in the following analysis to enable ananalytical solution to be obtained:Eq.(21)then givesÀZ UU odUU¼10νU2or4esinϕZ rr er2drð22Þwhich yields the analytical result1À1o¼10ν3U2or4esinϕðr3Àr3eÞð23ÞThe location of the jump at locations above point of impingementis given by the force balance(Eq.(10)),which is now written asU Rθ¼53γð1ÀcosβÞU oρr2e sinϕRθð24Þwhere the subscriptθis used to emphasise that the location of thejump depends on the value of the angle.Equating(23)and(24)togfilmjumpOFig.7.Geometry of impinging jet.(a)Side view,(b)end view.O marks the point ofimpingement.T.Wang et al./Chemical Engineering Science102(2013)585–601590find r ¼R θgives1R θ¼1θ3U o ρr 2e sin ϕ¼1o þ10ν3r 4e U 2osin ϕðR 3θÀr 3eÞð25ÞSubstituting (16)and (19)into (25)eliminating r e and takingU ¼U R in (19)and _m¼ρU o πr o 2gives R 4θ¼r o sin ϕ3À0:3r 2o _m sin 6ϕπμð1þcos ϕcos θÞ"#R θþ0:18_msin 9ϕπ3ρμγð1Àcos βÞð1þcos ϕcos θÞð26ÞThis quartic in R θcan be solved numerically or analytically (seeWang et al.,2013).A useful approximation for illustrative purposes is obtained by setting 1/U o and r e 3to zero from (25)and using (16)to eliminate r e ,giving R 4θ¼950r 6e U 3o sin 3ϕρ2μγð1Àcos βÞ¼sin 9ϕð1þcos ϕcos θÞ9U 3or 6o ρ2μγð1Àcos βÞð27ÞFor the conditions considered in this paper,Eq.(27)gives close agreement with numerical solutions to (26),con firming that the above assumptions are justi fied.The effect of impingement angle is plotted in Fig.8(a)for the case of a 4mm diameter water jet impinging on Perspex (contact angle ¼72.51)at a flow rate of 0.1kg s À1.The location of the film jump is plotted in Cartesian co-ordinates with O as the origin,where x ¼R θsin θand y ¼R θcos θÀr o cot ϕ.The plots show that a jet inclined downwards (ϕo 901)projects a small fraction of the flow above the plane of impingement,whereas those inclined upwards project a larger fraction upwards,so that the film jump is located further uptheFig.8.Effect of impingement angle on predicted film jump shape for 100g s À1water jet from 4mm nozzle impinging on a vertical Perspex surface.(a)Ignoring gravity;(b)considering gravity.Cartesian co-ordinates centred on the point of impingement.ϕValues indegrees.Fig.9.Predicted maximum half-width of impingement zone for obliquely impinging jets.d N ¼4mm,Perspex surface,gravity neglected.(a)Downward jet,(b)upward jet.ϕValues in degrees.T.Wang et al./Chemical Engineering Science 102(2013)585–601591。
舌下给药
International Journal of Pharmaceutics 457(2013)168–176Contents lists available at ScienceDirectInternational Journal ofPharmaceuticsj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /i j p h a rmElectrospun drug loaded membranes for sublingual administration of sumatriptan and naproxenPetr Vrbata a ,Pavel Berka a ,Denisa Stránskáb ,Pavel Doleˇz al a ,∗,Marie Musilováa ,Lucie ˇCiˇz inskáa a Department of Pharmaceutical Technology,Faculty of Pharmacy in Hradec Králové,Charles University in Prague,Czech RepublicbElmarco Ltd.Co.,Liberec,Czech Republica r t i c l e i n f o Article history:Received 17July 2013Received in revised form 27August 2013Accepted 28August 2013Available online 16September 2013Keywords:Electrospinning Nanofibre Migraine Sublingual Sumatriptan Naproxena b s t r a c tSublingual administration of active pharmaceutical substances is in principle favourable for rapid onset of drug action,ready accessibility and avoidance of first pass metabolism.This administration could prove very useful in the treatment of migraines,thus two frequently used drugs were selected for our study.Sumatriptan succinate,naproxen,and its salt as well as combinations of these were incorporated into nanofibrous membranes via the electrospinning process.DSC measurements proved that the resulted membranes contained non-crystalline drug forms.SEM imaging approved good homogeneity of diameter and shape of the membrane nanofibres.The nanofibrous membranes always showed the rapid and mutually independent release of the tested drugs.The drugs exhibited very high differences in sublingual permeation rates in vitro ,but the rates of both substances were increased several times using nanofibrous membranes as the drug carrier in comparison to drug solutions.The released drugs subsequently permeated through sublingual mucosa preferentially as non-ionized moieties.The prepared nanofibrous membranes proved very flexible and mechanically resistant.With their drug load capacity of up to 40%of membrane mass,they could be very advantageous for the formulation of sublingual drug delivery systems.©2013Elsevier B.V.All rights reserved.1.IntroductionMigraine is a chronic relapsing brain disorder that affects about 12%of the Western population.It occurs as a unilateral headache,often accompanied by other symptoms,including nau-sea,vomiting,photophobia,and phonophobia,lasting from 4to 72h (Arulmozhi et al.,2005).In 15%of cases,a migraine headache is preceded by the aura,a transient neurological dysfunction,which is usually characterized by visual and/or sensory symptoms.Migraine has a very strong social impact,influencing quality of life and work productivity (Ramdan and Buchanan,2006).Sumatriptan is the most frequently used member of triptans commonly prescribed for the treatment of migraine headaches (with or without aura).Suma-triptan could be also administered together with NSAID naproxen sodium,which brings higher benefits to diminish symptoms of migraine than usage of either of the drugs separately.Abbreviations:SUS,sumatriptan succinate;NAPS,naproxen sodium;NAP,naproxen.∗Corresponding author.Tel.:+420495067438.E-mail address:dolezal@faf.cuni.cz (P.Doleˇz al).Actual dosage forms of sumatriptan are pills (50and 100mg),subcutaneous injection (4and 6mg),and nasal spray (10and 20mg).Succinate salt is well soluble in water,but its bioavailabil-ity (BA)after oral administration is only about 14%.Nasal spray administration of a sumatriptan base has a BA of about 16%(Imitrex,2013).Low BA following oral administration,relatively short half-life,and a requirement for the fast onset of action instigated the research for a new route of administration of this drug.A sublingual route of administration could be very advantageous in the given case.Although a relatively small surface area and dif-ficulties with the dosage form (permanently washed by saliva,and involuntary swallowing of liquids greater than 200L)have limited this site for drug administration so far,it possesses many advanta-geous characteristics.Very thin mucosa (100–200m),good blood supply,perfect accessibility,non-invasiveness of administration,and potential ease of removal encouraged research efforts in this area.The fast onset of systemic drug action is also very important,and the avoidance of the first-pass metabolism is in many cases essential (Hearnden et al.,2012;Bayrak et al.,2011;Patel et al.,2011a,b ).Moreover,this way of administration is also suitable for small children,elderly people,and other patients with swallowing or digestion problems (Patel et al.,2011b ).0378-5173/$–see front matter ©2013Elsevier B.V.All rights reserved./10.1016/j.ijpharm.2013.08.085P.Vrbata et al./International Journal of Pharmaceutics457(2013)168–176169Currently,there are several sublingual preparations,mostly based on fast dissolving(disintegrating)tablets,films,wafers,and sublingual sprays commercially available,and new dosage forms are being tested(Patel et al.,2011a;Hearnden et al.,2012).A relatively new and very promising technology for the for-mulation of sublingual drug delivery systems is based on the use of electrospun drug loaded nanofibrous membranes(Nagy et al., 2010;Yu et al.,2010a,b;Stranska et al.,2012).Electrospinning is a unique technique for the preparation of ultra-finefibres with the diameter size going down to nanometres.Although the principle of this procedure has been known for almost a century,it became a topic of great interest in the early1990s,when Reneker and co-workers demonstrated the possibility of electrospinning a wide range of polymers(Reneker and Chun,1996;Frenot and Chronakis, 2003).Nowadays,most of linear synthetic and also natural polymeric compounds can be easily electrospun into nanofibres(Frenot and Chronakis,2003;Agarwal et al.,2013).A very important moment for further development was the invention of a large-scale produc-tion device the Nanospider TM which makes it easier to scale up production for commercial processing(Jirsak et al.,2005).Never-theless,scaling up production of every individual product is always challenging,especially in pharmaceutical industry.Nanofibres,or rather nanofibrous membranes,have already found their application in many disciplines.Thanks to their unique properties,namely high surface area to volume ratio,high nanoporosity,high mechanical strength,and structural similarity to an extracellular matrix,they attract a lot of attention within tech-nical disciplines,but also in biomedicine and pharmacotherapy and new dosage formulation types(Agarwal et al.,2013;Leung and Ko, 2011;Nagy et al.,2012).In the biomedicalfield,nanofibresfind usage in the forma-tion of tissue engineering scaffolds(Cao et al.,2009;Leung and Ko,2011),wound dressing(Zhang et al.,2009;Leung and Ko, 2011;Sell et al.,2009),vascular grafts(Zhang et al.,2009;Sell et al.,2009),and drug delivery systems(Leung and Ko,2011; Chakraborty et al.,2009;Meinel et al.,2012).Many kinds of drugs have already been incorporated into the nanofibrous mats and then successfully released from them without a significant loss of their activity.Among low molecular drugs antibiotics(Kenawy et al.,2002;Kim et al.,2004),non-steroidal anti-inflammatory drugs(NSAID)(Taepaiboon et al.,2006;Kenawy et al.,2007; Huang et al.,2012),vitamins(Taepaiboon et al.,2007;Madhaiyana et al.,2013),chemotherapeutics(Xu et al.,2009),and many oth-ers have already been described.Higher molecular compounds, mostly protein based,were also shown to be effectively released from nanofibres(Maretschek et al.,2008;Han et al.,2012).In our work,we focused on the limits of sublingual administra-tion of sumatriptan and naproxen,in the context of permeability of sublingual mucosa in vitro,then on the examination of suitable polymers for co-formulation of both the drug-loaded electrospun membranes and estimation of formulation parameters for release profiles potentially suitable for anti-migraine action.2.Materials and methods2.1.MaterialsSumatriptan succinate(SUS)was kindly donated by Teva Czech Industries s.r.o.(Opava,CZ).Naproxen(NAP),naproxen sodium(NAPS)and chitosan(CHI,Mw60,000–120,000)were pur-chased from Sigma–Aldrich(Prague,CZ),polyacrylic acid(PAA,Mw 450,000),poly--caprolacton(PCL,Mw100,000)were purchased from Scientific Polymer Products(New York,USA),polyvinylalco-hol(PVA,type Z220,viscosity of4wt%water solution at20◦C 11.5–15mPa s)from Nippon Gohsei(Düsseldorf,GE).Acetic acid, formic acid,phosphoric acid,and potassium dihydrogen phosphate were supplied by Penta Chemicals(Prague,CZ).The aqueous solutions were prepared with purified water.All the chemicals were used as received without further purification.2.2.Methods2.2.1.Formulation of drug loaded electrospun membranesThe nanofibrous mats were produced by electrospinning from polymer solutions using Nanospider TM technology(Jirsak et al., 2005).Chitosan was dissolved in a mixture of acetic acid and water2:1in a concentration of2.25%;PVA was dissolved in a water:phosphoric acid mixture(99.3:0.7)in a concentration of11%; PAA was dissolved in a0.1M sodium chloride solution in a con-centration of6%with the addition of-cyclodextrin1.2%(as a cross-linking agent);PCL was dissolved in a mixture of acetic acid: formic acid(2:1)in a concentration of12%.The active substances were added in concentrations ranging from5%to30%related to the mass of the polymer in the solution for electrospinning.All the chemicals were stirred until homogenous solutions were obtained,and then poured into the container of an elec-trospinning device.Spinning electrode was in a shape of wire, electrospinning is nozzle free.After the application of a high volt-age,nanofibres were formed and then collected on a spunbond textile covering the collector plate.Speed of spunbond movement through the device determines nanofibrous layer thickness(g/m2). In the case of water-soluble polymers(PVA,PAA)cross-linking was performed.After electrospinning process the membranes were thermally treated in a drying oven at130◦C for15min in the case of PVA and at140◦C for20min in the case of PAA.2.2.2.CharacterizationThe morphology of prepared nanofibrous membranes was eval-uated by scanning electron microscopy–NOVA NanoSem230(FEI, USA)with maximal resolution up to1.3nm at30kV and magnifi-cation up to1,000,000times.The differential scanning calorimetry(DSC)analyses were car-ried out using a200F3MAJA calorimeter(NETZSCH,Germany). Samples were heated at speed5◦C/min from20◦C to200◦C.The nitrogen gasflow rate was set at40mL/min.2.2.3.Drug release evaluationDrug release measurements were conducted in a water bath under a constant temperature(36.5±0.5◦C)and permanent stir-ring(magnetic bar;200rpm).Pieces of membrane5cm×4cm (20cm2)were precisely weighed and then placed inside vials.The vials werefilled with20mL of a pre-tempered phosphate buffered solution of pH7.4(PBS)as an acceptor phase,and placed inside the water bath.The samples of the acceptor phase(0.6mL)were with-drawn in pre-determined time intervals(5,10,15,and30min,1,2, 4,8,and24h)and the pertinent volume was replaced with a fresh buffer.2.2.4.In vitro permeation experimentsIn vitro drug permeation experiments were performed using a porcine sublingual mucosa.The basic principles were derived from analogical experiments used in transdermal permeations,previ-ously described in detail(Patel et al.,2011a).Pieces of mucosa were obtained from the lower side of fresh porcine tongues(supplied from a local slaughterhouse) by surgically removing the muscle and connective tissues.After preparation,large pieces of obtained mucosa were stored in a 0.9%sodium chloride solution with the addition of sodium azide (0.002%).The processed sublingual membranes were about0.4mm170P.Vrbata et al./International Journal of Pharmaceutics457(2013)168–176Fig.1.Diffusion and permeation cell.in thickness.They were cut into pieces(2cm×2cm)andfixed between a donor and an acceptor compartment of diffusion cells (Fig.1).The actual area exposed for permeation was2cm2.The PBS(pH7.4)was used as an acceptor phase.Permeation was con-ducted in a water bath–temperature(36.5±0.5◦C)and stirring with magnetic bar.In vitro permeation of SUS,NAP and NAPS was evaluated using the donor solutions(PBS,pH6.8,0.5mL)with selected concentra-tions(1%,3%,6%for SUS;1%,2%,3%,10%for NAPS)and the tested nanofibrous membranes.Samples(0.6mL)of the acceptor phase were withdrawn in pre-determined time intervals(15,30min,1, 2,4,6,and8h)and replaced with a fresh buffer.The samples were briefly stored in a refrigerator until HPLC determination of investi-gated substances was performed.All drug release measurements were performed in triplicate,and in the case of in vitro sublin-gual permeation experiments,four replicates were performed.The values presented below are calculated as the means with their standard errors of the means(SEM).The stability pre-tests of the drugs were carried out in arti-ficial saliva(pH6.8)and an isotonic phosphate buffer(pH7.4). Low stability of the drugs in one of these mediums would be very limiting for potential use.The obtained results showed no signifi-cant decrease in the concentration of the drugs during a24h period.2.2.5.HPLC analysisDrug concentrations in the samples of the acceptor phase were determined using HPLC set Agilent Technologies1200(USA) equipped with an auto sampler ALS1329A,UV/VIS detector VWD G1414B,and an isocratic pump G1310A.2.2.5.1.Sumatriptan.The mobile phase was a mixture of ammo-nium phosphate(0.05M)and acetonitrile(84:16,v/v),pH was adjusted to3.0with the addition of0.1M phosphoric acid.Theflow rate was set at1.5mL/min.The method of Nozal et al.(2002)was modified to avoid interference from skin residues at the retention time of sumatriptan at227.4nm;the detection wavelength was set at282.7nm(Femenıa-Font et al.,2005).Separation was carried out at30◦C with the use of250mm×4.6mm,a reverse-phase column packed with5m C18silica particles(Zorbax Eclipse XDB C18). 2.2.5.2.Naproxen.The mobile phase was a mixture of potassium dihydrogen phosphate(0.01M;pH adjusted to2.5with the addi-tion of0.1M phosphoric acid)and acetonitrile(55:45,v/v).Theflow rate was set at1.5mL/min.Separation was carried out at25◦C,on a150mm×4.6mm,reverse-phase column packed with5m C18 silica particles(Zorbax Eclipse XDB C18).The detection wavelength was set at230nm.2.2.6.Data treatmentThe primary data from HPLC assay of the samples were further corrected for sampling and replacement of the pure acceptor phase. The amounts of the drug passed through the1cm2of sublingual mucosa were obtained.The cumulative amount of the drug vs.time dependence was used to calculate the pertinent slope values of the linear part of the concerned dependence with linear regression. The values obtained were understood as the individualflux values J[g/cm2/h]of the pseudosteady state permeation.Theflux values means and standard error of the means(SEM)(number of replicates n=4)were calculated.3.Results and discussionIn this paper,we focused on membranes ensuring longer con-tact time of the drug with absorption mucosa using a non-soluble (removable)membrane.Membrane prevents the leaking of a drug to an oral cavity and swallowing the drug,whilst masking the unpleasant taste.3.1.Scanning electron microscopyThe prepared nanomembranes were analyzed by scanning elec-tron microscope for averagefibre diameter and uniformity of the membranefibres.This characterization confirmed that the diam-eters of all the membrane nanofibres were within the nanometre scale and of good shape and diameter uniformity(Fig.2).It can be concluded that incorporation of the drugs into the nanofibrous membranes brought no free particles of the drugs,neither on the surface of nanofibres,nor particles larger than nanofibre diam-eter embedded within the mass of thefibres.It is important as evidence of well-tuned electrospinning parameters that make it possible to obtainfibres without loss of the drug,and with good shape homogeneity.Very similar images were also obtained for all other prepared membranes.3.2.Differential scanning calorimetry(DSC)The physical state of the carrier polymers and the incorporated drugs was investigated by DSC measurements.The DSC thermo-grams of chosen samples are shown in Figs.3–5.The thermogram of crystalline naproxen exhibits a strong endothermic peak at 157.1◦C,while no melting peak was present on thermograms of nanofibrous mats containing5%or30%of incorporated naproxen. This result proves that naproxen in the tested nanofibrous mats is present in an amorphous state,or more likely,homogeneously dispersed in the polymer matrix offilaments.Moreover,no glass transition peak of carrier polymer was found.Thisfinding is also important,because polymer crystallinity plays an important role in interactions with water,and therefore also drug release(Natu et al.,2010).Similar results were concluded from measurements with suma-triptan succinate.The crystalline form of sumatriptan succinate provided an endothermic peak at169.7◦C,no melting peak or glass transition peak were found on the other thermograms.3.3.Release of the drugs from nanofibrous membranesRelease characteristics of the investigated drugs were tested and evaluated by the complete immersion of the mats in the release medium.P.Vrbata et al./International Journal of Pharmaceutics457(2013)168–176171Fig.2.SEM images of the prepared membranes.A:Chitosan–blank;B:chitosan–containing SUS(5%);C:chitosan–containing NAP(5%);D:PVA–blank;E:PVA–containing SUS(5%);F:PVA–containing NAP(5%).Several different polymers with expected fast drug release were chosen.The polymer selection was further influenced by the intended purpose of their use in the sublingual dosage form. Bioadhesivity and biocompatibility of polymers were therefore important.The amounts of the incorporated drugs ranged from5%to30%of mass of the polymer in an electrospinning solution.The influence of drug concentrations in the nanofibres on the release profiles of the drugs was also evaluated,and is discussed later.The release of SUS from three different hydrophilic polymers–PVA,CHI,and PAA was tested.In all of the cases,burst release of the drug was observed with more than90%of the total releasable amount of the drug being dissolved in an acceptor phase within thefirst10min of the experiments(Fig.6).The amount of the drug released then remained at the same level for up to a further 24h.The release of NAP from three hydrophilic(CHI,PVA,PAA) and one hydrophobic polymer(PCL)was tested.All of the poly-mers provided burst release of naproxen.Similarly to sumatriptan, more than90%of the releasable drug was dissolved in the acceptor phase within10min(Fig.7).Interestingly,the membranes made of hydrophobic PCL also showed a very fast release of NAP.All of the membranes under investigation showed suitable drug release for formulation of a sublingual dosage form for whose requirement of fast drug release is of great importance(Hearnden et al.,2012).Under the given conditions,the release profiles of NAP and NAPS from electrospun mats did not show any evident differences, although the solubility and rate of dissolution of the crystalline form of the given substances in the acceptor mediumusedFig.3.DSC profiles of A:sumatriptan succinate(crystalline powder);B:PVA+sumatriptan suc.20%(nanofibrous membrane);C:PVA(nanofibrous membrane without drug); D:PVA(powder).172P.Vrbata et al./International Journal of Pharmaceutics 457(2013)168–176Fig.4.DSC profiles of A:naproxen (crystalline powder);B:PVA +naproxen 30%(nanofibrous membrane);C:PVA +naproxen 5%(nanofibrous membrane);D:PVA (nanofibrous membrane without drug);E:PVA (powder).Fig.5.DSC profiles of A:naproxen (crystalline powder);B:chitosan +naproxen 5%(nanofibrous membrane);C:chitosan (nanofibrous membrane without drug);D:chitosan (powder).Fig.6.The release profiles of sumatriptan succ.from nanofibrous membranes containing 5%of the drug made of polyvinylalcohol (PVA),chitosan (CHI),and poly-acrylacrylate (PAA)(n =3;mean ±SEM).Fig.7.The release profiles of naproxen from nanofibrous membranes containing 5%of the drug made of polyvinylalcohol (PVA),chitosan (CHI),polyacrylacrylate (PAA),and poly--caprolacton (PCL)(n =3;mean ±SEM).P.Vrbata et al./International Journal of Pharmaceutics457(2013)168–176173Fig.8.A:Release of sumatriptan succinate from PVA nanofibrous membranes containing5%,10%,or20%of the drug incorporated.B:Release of naproxen from PVA nanofibrous membranes containing5%,10%,or30%of the drug incorporated.differs greatly.It seems to be an indirect evidence of the fact that drug incorporation into nanofibres by the electrospinning process has brought dramatic changes in solubility properties,and that an initial difference of the drug solubilities is levelled in direction to higher solubility.In most cases,40–80%of the theoretically calculated amount of the drugs loaded in nanofibrous membranes were released,varying with the polymer used.Differences between the amounts of drugs incorporated and released were probably caused by different sol-ubility of the polymeric nanofibrous membranes in the acceptor phase.Srikar et al.(2008)assumed that substances(dyes in their study) might only be released from the available surface layers of the poly-mer,including surfaces of nanopores,whereas the drug inside the polymer bulk will not be released at all.The results of our experi-ments corroborate this assumption,because in no experiment was complete release of the incorporated drugs from membranes insol-uble in the acceptor phase achieved.This assumption also correlates with otherfindings that higher percentages(not only amounts)of the drugs were released from the nanofibrous mats containing higher levels of the drug per mass of polymer(Fig.8).When a higher level of a drug is incorporated,a higher proportion of the drug is likely to be deposited next to the fibre surfaces,and is therefore available for release.The membranes highly soluble in acceptor phase allowed almost complete release of the drugs theoretically incorporated into the membranes.Further reduction in the amount of the drugs released was probably caused by cross-linking of polymer chains.Cross-linking agents could bind incorporated drugs to the polymeric chains,ren-dering the drug un-releasable,and thus reducing the total amount of drug available.Theoretically,the bonding of drug molecule to polymer chains can form new,barely soluble molecules.The reduc-tion was most apparent in the case of PAA,where the released drug in some cases represented only about30%of the incorporated amount,while the amount of drug released from non-cross-linked nanofibrous mats reached almost the entire incorporated drug.In the case of simultaneous release of two different drugs,when both of the drugs were incorporated either in one single nanofi-brous layer or in multilayered electrospun membrane separately, the release of one drug did not influence the release of the other (Fig.9).In the experiments dealing with maximal drug load capacity, the maximal level of drug incorporated in nanofibrous membranes using this electrospinning method was found to be around40% of the membrane mass.With further increase in a drug concen-tration the electrospinning process was disturbed and structural defects multiplied(detected by SEM)or the process was completely disrupted.3.4.Permeation of the drugsPermeation of both the drugs through a porcine sublingual mucosal membrane was tested using drug solutions atfirst,because sublingual permeability of neither SUS nor NAP had already been sufficiently explored.Sumatriptan succinate is a hydrophilic substance.Although its molecular weight is relatively low,it exerted slow and incomplete permeation through the sublingual mucosa.For instance,usage of saturated solutions(30mg/0.5mL,pH7.4)as donors yielded only about0.1mg of SUS totally found in the acceptor phase(20mL) within8h,e.g.only0.33%of the drug loaded in a donor compart-ment.Because of very slow permeation(pH7.4donor),the influence of ionization of SUS(the p K a values are4.21,5.67,9.63,>12)on permeation rate was explored.Permeation was evaluated using donor solutions of pH values3.9,7.4,12.0.The highest concentra-tions in the acceptor phase and highest pseudosteady statefluxes were obtained at pH12.0,where sumatriptan occurs mostly in the unionized form as a sumatriptan base.The lowest permeation rate was found with donors of pH3.9,where the sumatriptan succi-nate molecule is fully ionized(Fig.10and Table1).It is in good agreement with the theory of passive permeation through most biological membranes.Results of a similar character wereobtainedFig.9.Simultaneous release of naproxen sodium and sumatriptan succinate from chitosan nanofibrous membranes(n=3;mean±SEM).174P.Vrbata et al./International Journal of Pharmaceutics 457(2013)168–176Fig.10.Permeation of sumatriptan through a porcine sublingual membrane using donor solutions (6%,0.5mL)of three different pH (3.9,7.4and12.0).Fig.11.Permeation of sumatriptan through a porcine sublingual membrane.Donors:PVA nanofibrous membrane 2mg,solution 1%(sol 5mg),solution 6%(sol 30mg).in a study with nicotine,where the differences of permeation rates at various pH values (expressed as cumulative amounts)were even more significant (Chen et al.,1999).The nanofibrous PVA membranes containing 20%of SUS were placed on the sublingual mucosa as the donor samples,and con-centrations of the permeated drug in acceptor compartments were measured.The results showed (Fig.11)that permeation from the nanofibrous donor was much faster compared to the solution con-taining 5mg of the drug in 0.5mL of donor (e.g.1%),although the amount of the drug in the solution was more than 2times higher than in the nanofibrous membranes.Moreover,within the initial 2h period,SUS permeation from nanofibres was even faster thanTable 1The sublingual permeation flux values.Sample (SUS)Flux (g/cm 2/h)Sample (NAPS)Flux (g/cm 2/h)Nano PVA –2mg 4.39±0.56Nano PCL 5mg 180.59±14.05Sol pH 7.4–5mg 2.71±1.00Sol 5mg 77.30±16.56Sol pH 12–30mg 13.47±3.47Sol 10mg 185.95±19.40Sol pH 7.4–30mg 10.32±2.72Sol 16mg 521.26±14.03Sol pH 3.9–30mg6.43±2.47Sol 50mg2277.31±41.71Fig.12.Amounts of sumatriptan permeated.Donors:PVA nanofibrous membrane 2mg,solution 1%(sol 5mg),solution 6%(sol 30mg,pH 12).from the saturated solution.This finding can be explained by a much higher concentration of the drug presented at the very large interface of nanofibre/mucosa.It is possible to imagine an exposed mucosal layer that is fully saturated with the drug released from the nanofibres,and an immediate replacement of permeated-off drug from nanofibrous storage.This situation is quite different in com-parison with the drug solution donor sample.Nanofibres probably served as a reservoir for surface facilitated drug release supplying the carrier/mucosa interface with a higher efficiency than was the case with solutions.As results in Fig.12show the transmucosal drug permeation was increased about 5times when the drug is loaded in nanofibrous membranes,compared to the highly concentrated solutions used as a donor.The increase in released and subsequently permeated drug amounts in percentages of initially loaded amounts is substantial from a practical point of view.We consider the necessary permeated dose of SUS should reach at least 4mg (or rather 6mg)of the drug.It represents an equivalent of a subcutaneously administered dose of SUS with a bioavailability of about 96%(Imitrex,2013).Thus,if the permeated amount of SUS from the nanofibrous donor was about 4%of the loaded dose,then about 100mg of SUS would have to be administered (on 20cm 2,which is the estimated area size of the sublingual mucosa available for administration,and also the size of the intended membrane formulation).This require-ment could be technologically realizable.For instance,to obtain 100mg of API for delivery the nanomembrane weight would have to be about 250or 300mg of nanofibres made of one or more poly-mers.The membrane would have to be produced of a high drug load and a high mass per area (g/m 2).The membranes could be lay-ered and then pressed to fix them.This reservoir would be covered by an impermeable layer on one side.We also take into account a possible addition of an adhesive at the edges of a final preparation to ensure a good and long term contact at a place of absorption.Further improvement could be achieved by the use of a suma-triptan base for the formulation of drug loaded nanofibrous membranes,because this form of the drug is more permeable across the sublingual membrane,as illustrated in Fig.10.Penetration enhancers are another applicable possibility to improve the per-meation rate.They can be directly incorporated into electrospun membranes,and released simultaneously with a drug affecting its permeation.。
分析化学考研面试问题。
药物分析实验典型问题1、鉴别检查在药品质量控制中的意义及一般杂质检查的主要项目是什么? What are thepurposes of drug identification and test? What are the usual items of drug tests?.2、比色比浊操作应遵循的原则是什么? What are the standard operation procedures forthe clarity test?3、试计算葡萄糖重金属检查中标准铅溶液的取用量。
How much of the lead standardsolution should be taken for the limit test for heavy metals in this experiment?4、古蔡氏试砷法中所加各试剂的作用与操作注意点是什么? What precautions shouldbe taken for the limit test for arsenic(Appendix VIII J,method 1)? And what is the function for each of the test solutions added?5、根据样品取用量、杂质限量及标准砷溶液的浓度,计算标准砷溶液的取用量。
Figure outthe amount of the arsenic standard solution that should be taken for the limit test for arsenic(Appendix VIII J,method 1) (0.0001%) in this experiment with the specified quantity of 2.0 g of sample.6、炽灼残渣测定的成败关键是什么?什么是恒重?What is the key step during thedetermination of residue on ignition? What does ‘ignite or dry to constant weight’mean?7、盐酸普鲁卡因的鉴别原理是什么?What are the principles of the identification ofProcaine Hydrochloride.8、盐酸普鲁卡因注射液中为什么要检查对氨基苯甲酸?Why is the limit of4-aminobenzoic acid tested for Procaine Hydrochloride?9、薄层色谱法检查药物中有关物质的方法通常有哪几种类型?本实验属于哪种?与其它方法有何异同点? How many kinds of the limit tests for related compounds are there?What are the differences between them? Which one is used for the limit test of 4-amino-benzoic acid in Procaine Hydrochloride Injection?10、醋酸氢化可的松的鉴别原理是什么?What are the principles of the identification ofhydrocortisone acetate?11、甾体激素中“其它甾体”检查的意义和常用方法是什么?What are the commonly usedmethod for and the significance of the limit test for other steroids for the steroidal drugs?12、哪类甾体激素可与四氮唑蓝产生反应,是结构中的何种基团参与了反应,反应式是什么?What kind of steroidal drugs can react with the alkaline tetrazolium blue TS?What is the chemical reaction equation?13、氯贝丁酯的鉴别原理是什么?What are the principles of the identification ofclofibrate?14、氯贝丁酯中为什么要检查对氯酚?其方法及原理是什么?Why is the limit ofp-Chlorophenol tested for clofibrate? What kind of method is employed for the test and what is the principle?15、气相色谱法检查杂质有哪些方法,试比较各种方法的特点?How many types ofmethods are there for the test of related compounds by the gas chromatography?What are the differences between them?16、抗生素类药物的鉴别和检查有何特点?What are the characteristics for theidentification and tests of antibiotics?17、钠盐的焰色反应应注意什么?What precautions should be taken during the flamereaction of sodium salts?18、本品吸收度检查的意义是什么?What is the purpose of the light absorption tests forbenzylpenicillin sodium?19、药物晶型测定的常用方法有哪些,各有什么特点?What are the commonly usedmethods for the test of polymorphism? And what are the characteristics of each of them?20、吸收系数测定方法与要求?What are the standard operation procedures for theestablishment of specific absorbance?21、写出异烟肼与溴酸钾的滴定反应式和滴定度的计算过程。
TransverseSpinPh...
Transverse Spin Physics:Recent DevelopmentsFeng Yuan1,2∗1-Nuclear Science Division,Lawrence Berkeley National Laboratory,Berkeley,CA94720,USA 2-RIKEN BNL Research Center,Brookhaven National Laboratory,Upton,NY11973,USATransverse-spin physics has been very active and rapidly developing in the last fewyears.In this talk,I will briefly summarize recent theoretical developments,focusingon the associated QCD dynamics in transverse spin physics.There have been strong experimental interests on transverse spin physics around the world,from the deep inelastic scattering experiments such as the HERMES collaboration at DESY,SMC at CERN,and Hall A and CLAS at JLab,the proton-proton collider experiment from RHIC at Brookhaven,and the very relevant e+e−annihilation experiment from BELLE at KEK.One of the major goals in transverse spin physics is to study the quark transversity distribution,the last unknown leading-twist quark distribution in nucleon.As discussed by several talks in this conference,we can study the quark transversity distributions from many processes[1,2,3,4,5],such as the double transverse spin asymmetry in Drell-Yan lepton pair production in pp collision,single hadron and two hadron production in semi-inclusive deep inelastic scattering,and other processes.We are now starting to have afirst glimpse about the quark transversity distribution from the experiments(see from example[5]).Besides the quark transversity distribution,the transverse spin physics also opened a new window to explore the partonic structure of nucleon,the so-called transverse momen-tum dependent(TMD)parton distributions[4].TMD parton distribution is an exten-sion to the usual Feynman parton distributions.These distributions allow us to study the three-dimension picture of partons inside the nucleon,and they are also closely related to the generalized parton distributions[6]and the parton orbital angular momenta.Es-pecially,the single transverse spin asymmetry(SSA)phenomena in high energy hadronic processes have attracted many theoretical and experimental investigations.The SSA is defined as the asymmetry when one of the hadrons’transverse spin isflipped,A N∼(dσ(S⊥)−dσ(−S⊥))/(dσ(S⊥)−dσ(−S⊥)).It has been a great theoretical challenge in the understanding of these phenomena.This is because the leading partonic contribution to the SSA vanish in the leading order,whereas the experimental observation show that these SSAs are in tens of percentage in the forward scattering of the polarized nucleon.Recent theoretical developments have made great progress in the exploration of the underlying physics for the single spin phenomena.It is impossible to cover all these exciting physics in this short talk.Rather,I would like to focus on one important subject,i.e.,the nontrivial QCD dynamics associated with transverse spin physics:the QCD factorization, and the universality of the parton distributions and fragmentation functions.Among those TMD parton distributions and fragmentation functions,two functions have been mostly discussed:the Sivers quark distribution and the Collins fragmentation func-tion.The Sivers quark distribution represents a distribution of unpolarized quarks in a ∗This work was supported in part by the U.S.Department of Energy under contract DE-AC02-05CH11231.We are grateful to RIKEN,Brookhaven National Laboratory and the U.S.Department of Energy(contract number DE-AC02-98CH10886)for providing the facilities essential for the completion of this work.transversely polarized nucleon,through a correlation between the quark’s transverse mo-mentum and the nucleon polarization vector.The Collins function represents a correlation between the transverse spin of the fragmenting quark and the transverse momentum of the hadron relative to the “jet axis”in the fragmentation process.Although they both belong to the so-called “naive-time-reversal-odd”functions,they do have different universality prop-erties.For the quark Sivers function,because of the initial/final state interaction difference,they differ by signs for the SIDIS and Drell-Yan processes [7,8,9,10].On the other hand,there have been several studies showing that the Collins function is universal between differ-ent processes,primarily in the SIDIS and e +e −annihilation [11,12,13,14],and recently in pp collisions [15].In the following,I will take the example of the Collins contribution to the azimuthal asymmetric distribution of hadrons inside a high energy jet in the transversely polarized pp collision to demonstrate this universality property,p (P A ,S ⊥)+p (P B )→jet (P J )+X →H (P h )+X ,(1)where a transversely polarized proton with momentum P A scatters on another proton with momentum P B ,and produces a jet with momentum P J .The three momenta of P A ,P B and P J form the so-called reaction plane.Inside the produced jet,the hadrons are distributed around the jet axis,where we define transverse momentum P hT relative to the jet axis.The correlation between P hT and the polarization vector S ⊥introduces the Collins contribution to the single spin asymmetry in this process.Figure 1:Gluon exchange diagrams contributions to the Collins asymmetry in pp collisions.The short bars indicate the pole contributions to the phase needed for a non-vanishing SSA.The additional two cuts in (d)cancel out each other.We need to generate a phasefrom the scattering amplitudes tohave a non-vanishing SSA.If thephase comes from the vertex asso-ciated with the fragmenting quarkand the final state hadron,or from the dressed quark propa-gator,it is easy to argue the universality of the Collins func-tion between this process and theSIDIS/e +e −process,because theyare the same.The main issueof the universality discussion con-cerns the extra gluon exchangecontribution between the specta-tor of the fragmentation process and hard partonic part.In Fig.2,we have shown all these inter-actions for a particular partonic channel qq →qq contribution,in-cluding the gluon attachments to the incident quarks (a,c),and final state balancing quark (d)and theinternal gluon propagator (b).The contributing phases of the diagrams in Fig.2come from the cuts through the internal propagators in the partonic scattering amplitudes.In Fig.2,we labeled these cut-poles by short bars in the diagrams.From the calculations,we will find that all these poles come from a cut through the exchanged gluon and the fragmenting quarkin each diagram,and all other contributions either vanish or cancel out each other.For ex-ample,in Fig.2(d),we show two additional cuts,which contribute however opposite to each other and cancel out completely.Therefore,by using the Ward identity at this particular order,thefinal results for all these diagrams will sum up together into a factorized form, where the cross section is written as the hard partonic cross section for q(S⊥)q →q(s⊥)q subprocess multiplied by a Collins fragmentation function.The exchanged gluon in Fig.2 is now attaching to a gauge link from the fragmentation function definition.Similar calcu-lations can be performed for the other two processes SIDIS and e+e−annihilation,and the same Collins function will be observed.This argument can also be extended to two-gluon exchange diagrams[15].The key steps in the above derivation are the eikonal approximation and the Ward iden-tity.The eikonal approximation is valid when we calculate the leading power contributions in the limit of P hT P J.The Ward identity ensure that when we sum up the diagrams with all possible gluon attachments we shall get the eikonal propagator from the gauge link in the definition of the fragmentation function.The most important point to apply the Ward identity in the above analysis is that the eikonal propagator does not contribute to the phase needed to generate a nonzero SSA.This observation is very different from the SSAs associated with the parton distributions, where the eikonal propagators from the gauge link in the parton distribution definition play very important role[4,7,8,9,10,16].It is the pole of these eikonal propagators that contribute to the phase needed for a nonzero SSA associated with the naive-time-reversal-odd parton distributions,which also predicts a sign difference for the quark Sivers function between the SIDIS and Drell-Yan processes.More complicated results have been found for the SSAs in the hadronic dijet-correlation[17,18],where a normal TMD factorization breaks down[19].The reason is that the eikonal propagators from the initial andfinal state interactions in dijet-correlation process do contribute poles in the cross section[18,19]. Because of this,the Ward identity is not applicable,and the standard TMD factorization breaks down,although a modified factorization may be valid if we modify the definition of the TMD parton distributions to take into account all the initial andfinal state interaction effects[17].In particular,there is a sign change between the SSAs in SIDIS and Drell-Yan pro-cesses[7,8],Sivers SSA|DY=−Sivers SSA|DIS.(2) This nontrivial result of the opposite signs between the above two processes will still hold when gluon radiation contributions are taken into account,where the large transverse mo-mentum Sivers function is generated from the twist-three quark-gluon correlation func-tion[20,21].It is of crucial to test this nontrivial QCD predictions by comparing the SSAs in these two processes.The Sivers single spin asymmetry in SIDIS process has been observed by the HERMES collaboration,and the planned Drell-Yan measurement at RHIC and other facility will test this prediction.Another interesting probe for the initial/final state interaction effects is the SSA in heavy quark and antiquark production in hadronic process.Because the heavy quark and antiquark can be detected by their decay products,their SSAs can be measured separately.The heavy quark and antiquark produced in short distance partonic processes will experience different final state interactions with the nucleon spectator due to their different color charges,and therefore the SSAs for heavy quark and antiquark will be different.Detailed calculationsshow that the difference could be as large as a factor of3if the quark-antiquark channel contribution dominates[22].In summary,the universality of the parton distribution and fragmentation functions are very different in the single transverse spin asymmetry.These properties are still under theoretical and experimental investigations.These important physics,together with other exciting features have shown that the transverse spin physics is playing a very important role in the strong interaction physics for hadronic spin physics.We will learn more about QCD dynamics and nucleon structure from these studies.References[1]K.Tanaka,these proceedings.[2]G.Goldstein,these proceedings.[3]M.Radici,these proceedings.[4]P.Mulders,these proceedings.[5] A.Prokudin,these proceedings.[6]T.Teckentrup,these proceedings.[7]S.J.Brodsky,D.S.Hwang and I.Schmidt,Phys.Lett.B530,99(2002);Nucl.Phys.B642,344(2002).[8]J.C.Collins,Phys.Lett.B536,43(2002).[9]X.Ji and F.Yuan,Phys.Lett.B543,66(2002);A.V.Belitsky,X.Ji and F.Yuan,Nucl.Phys.B656,165(2003).[10] D.Boer,P.J.Mulders and F.Pijlman,Nucl.Phys.B667,201(2003).[11] A.Metz,Phys.Lett.B549,139(2002).[12]J.C.Collins and A.Metz,Phys.Rev.Lett.93,252001(2004).[13]L.P.Gamberg,A.Mukherjee and P.J.Mulders,Phys.Rev.D77,114026(2008).[14]L.Gamberg,these proceedings.[15] F.Yuan,Phys.Rev.Lett.100,032003(2008);Phys.Rev.D77,074019(2008).[16] C.Pisano,these proceedings.[17] C.J.Bomhof,P.J.Mulders and F.Pijlman,Phys.Lett.B596,277(2004);Eur.Phys.J.C47,147(2006);JHEP0702,029(2007);A.Bacchetta,C.J.Bomhof,P.J.Mulders and F.Pijlman,Phys.Rev.D72,034030(2005);C.J.Bomhof and P.J.Mulders,arXiv:0709.1390[hep-ph].[18]J.W.Qiu,W.Vogelsang and F.Yuan,Phys.Lett.B650,373(2007);Phys.Rev.D76,074029(2007);W.Vogelsang and F.Yuan,Phys.Rev.D76,094013(2007).[19]J.Collins and J.W.Qiu,Phys.Rev.D75,114014(2007);J.Collins,arXiv:0708.4410[hep-ph].[20]X.Ji,J.W.Qiu,W.Vogelsang and F.Yuan,Phys.Rev.Lett.97,082002(2006);Phys.Rev.D73,094017(2006);Phys.Lett.B638,178(2006).[21] A.Bacchetta,these proceedings.[22] F.Yuan and J.Zhou,arXiv:0806.1932[hep-ph].。
Determination of the Surface Fractal Dimension for Porous Media by Capillary Condensation
Determination of the Surface Fractal Dimension for Porous Media by Capillary CondensationFumin Wang and Shaofen Li*Department of Chemical Engineering,Tianjin University,Tianjin300072,People’s Republic of ChinaWe describe several methods of evaluating the surface fractal dimension of porous media.Theseinclude the thermodynamic method and the fractal version of Frenkel-Halsey-Hill theory.Neither method yields accurate estimates of the fractal dimensions of porous solids under thewhole range of experimental scales.We propose a modified thermodynamic method that isrelatively simple but is significantly more accurate than Neimark’s relation from the adsorptionexperiments.Then we use these methods to estimate the surface fractal dimension of severalkinds of porous media.After a concrete analysis of the properties of topology and mercuryporosimetry,N2adsorption,and N2desorption processes for porous media,we conclude that thereal surface fractal dimension should be determined by D abs(from the adsorption isotherm),D des(from the desorption isotherm),and D m(from the mercury porosimetry)jointly as D real)D abs+(D m-D des).IntroductionFractal geometry has been widely used in many areas of modern science.The key quantity in fractal geometry is the fractal dimension D,which is an operative measure of the surface and structural irregularities of a given solid.The fractal dimension should be deter-mined first before we can use the concept and knowledge of fractal geometry to characterize the structure of a given solid.The experimental methods used for the determination of the surface fractal dimension of porous solids have been reviewed by Avnir et al.(1992).The most common techniques are the adsorption and mercury porosimetry methods.In addition,electron microscopy image analy-sis and scattering methods(light,X-rays,neutrons)have also been used to demonstrate surface roughness for porous materials(Martin et al.,1986;Aubert et al., 1986;Freltoft et al.,1986).In this paper we restrict our attention to calculating the surface fractal dimen-sion from adsorption measurements because they are the most commonly used methods to determine the fractal dimension D of solid materials.Perhaps one of the oldest methods of evaluating the surface fractal dimension is that based on the depen-dence of monolayer capacity on the adsorbate size, which was developed by Pfeifer and Avnir(1983). Although this method is simple,the fractal dimensions determined by this method are not always consistent, especially when the orientations of adsorbate molecules on the surface are different.Also,this procedure has some disadvantages related to evaluation of the mono-layer capacity and selection of suitable adsorbates in order to avoid the effects associated with adsorbate-adsorbate interactions(Jaroniec,1995).Moreover,in this method,one needs to evaluate the monolayer capacities of several adsorbates of different molecular sizes,which makes the experiment rather time-consum-ing.Because the molecules adsorbed play the role of the gauges,the range of scales available in this method is limited by the molecular sizes.These problems become particularly important for adsorption on some microporous solids that possess a high degree of surface irregularity(Jaroniec and Madey,1988).Pfeifer et al.(1991)developed an adsorption-based method for surface roughness determination in1991. The principle is to measure the variation in surface area of the material coated with a series of presorbed films. In this method,they assume that every point of the film surface has the same shortest distance z to the solid,so the film area S(z)is related to the film volume V(z)by When the surface of the solid is fractal,with fractal dimension D,V(z)is proportional to z3-D and,therefore, S(z)is proportional to z2-D,so one obtainsFrom eq2,one can get the fractal dimension by measuring the surface area of the adsorbed film with varied film thicknesses of z.However,the equidistance assumption,on which this method is based,is open to doubt.The surface tension wants to make the film-vapor interface as flat as possible,so as to minimize the surface area of the interface.One cannot ignore the effect of the surface tension,especially when the film thickness is large(Pfeifer and Cole,1990).From the simulation results of this method,we can see that the deviations are very large and the corresponding cor-relation coefficient is very small(Pfeifer et al.,1991). Another popular method for evaluating D is that given by the Frenkel-Halsey-Hill(FHH)equation, which in logarithmic form can be expressed as follows (Pfeifer and Cole,1990):where N is the amount adsorbed at the relative pressure P/P0and absolute temperature T andµis the so-called adsorption potential defined asUsing eq3,one can determine D from physical adsorp-tion measurements on the fractal surface.On the other hand,Neimark et al.(1992,1994) proposed the so-called thermodynamic method for cal-culating the fractal dimension D from the adsorption isotherm data.In this model,the fractal surface area*Author to whom correspondence should be addressed.S(z))d V/d z(1)S∝V(2-D)/(3-D)(2)ln(N))const-(3-D)ln(µ)(3)µ)RT ln(P/P)(4)1598Ind.Eng.Chem.Res.1997,36,1598-1602S0888-5885(96)00555-6CCC:$14.00©1997American Chemical Societywas related to the average pore radius as(Neimark,1992):and the surface area of the adsorbed film is calculatedaccording to the Kiselev equation:where X denotes the relative pressure and N max denotesthe amount adsorbed at X tending to unity.Theyardstick is measured in terms of the average radius ofcurvature of the meniscus at the interface betweencondensed adsorbate and gas by the Kelvin equation: The thermodynamic method proposed by Neimark(1992)and the method based on the FHH theoryproposed by Pfeifer and Cole(1990)have been comparedwith one another by Jaroniec(1995).The theoreticalanalysis shows that both methods are essentially equiva-lent.However,the simulation results using Neimark’srelation show that the range of scale in which fractalexists is rather limited,which makes us suspect itsvalidity and robustness.The objective of this work is to develop a more reliablescaling relation to determine surface fractal dimensionof porous materials using the capillary condensationdata.We also show that the new method,based onconcrete analysis of the properties of topology andcapillary condensation processes for porous media,ismuch more accurate than Neimark’s relation and coversa wide range of scales.Then the simulation results willbe compared with those of the references.TheoryMandelbrot(1982)gave a correlation of the area fora fractal surface and the volume circumscribed by thesurface:In case the fractal surface is measured on a Euclideanarea,the above relation can be changed into thesubsequent form by dimensional analysis:where k0is a factor relating surface area with the corresponding volume.Just as illustrated by Neimark(1992),a given fractalsurface can be approximated by its inscribed equicur-vature surface(IES)of varying mean curvature radius(MCR).The decrease of the MCR,r c,causes penetrationof the IES into surface indentations of smaller size.Inother words,with a decrease of r c,the IES repeats allthe peculiarities of the substratum relief.In the limitr c f0,the IES is the fractal surface with the same dimension as the surface fractal dimension of thesubstratum.So,the mean curvature radius of theinscribed equicurvature surfaces can be chosen as ayardstick for measurement of the fractal surface.The practical realization of this method can be provided by using the adsorption experiments.In the process of adsorption of nitrogen in porous media,the equilibrium interface between the liquid film and gas acts as the inscribed equicurvature surface.So, the surface area of the adsorbed film can be calculated according to the Kiselev equation(6).After assuming that the liquid cannot be compressed, one can get the following relation:Substitution of S E and V(X)into eq9by eqs6and10 gives the following expression:LetEquation11will be changed into the ensuring style Accordingly,from the adsorption isotherm of nitrogen in the region of capillary condensation,we can compute a series of A(X)and B(X),where r c(X)can be predicted by the Kelvin equation(7)and then the surface fractal dimension can easily be achieved.Results and DiscussionFor a given porous solid,the desorption isotherm does not always retrace the adsorption isotherm but lies above it over a range pressures,forming a hysteresis loop,before eventually rejoining the adsorption iso-therm.The fractal dimension determined by eq13can be calculated either from the adsorption isotherm or from the desorption isotherm.First,the simulation of surface fractal dimension for several samples has been made by eq13using the nitrogen adsorption and desorption data of the literature(Neimark et al.,1994), so that we can have a comparison with the simulation results by Neimark’s relation.The evaluation of the surface fractal dimension of SiO2(A)using eqs5and13 is illustrated in Figures1and2,respectively,as an example.The obtained results are reported in Table1. This table also includes the range of scale from which the D was calculated.The above calculations and analyses show that the results simulated by means of eq13for several kinds of porous materials totally fall in the range of2<D< 3,which is predicted by fractal geometry,so this method is comparatively reasonable among the methods used to determine the surface fractal dimensions.From these results one can conclude that the method in this work is reliable over a sufficiently wide range of scales from1to250nm.Neimark’s relation,however,is seemingly reasonable only over a rather narrow range of scales.This is caused by the defects in the scaling relation(5).We know,from eq9,that only when theln(S))const-(D-2)ln(r)(5)S(X))RTσ∫N(X)N max ln(X)d N(X)(6) r)-2σVLRT ln(X)(7) S1/D∼V1/3(8)S E (δ))kDδ2-D V D/3(9)V(X))[Nmax-N(X)]VL(10)-∫N(X)N maxln(X)d N(X)rc2(X))kD VLD/3σRT[(N max-N(X))1/3rc(X)]D(11)-∫N(X)N maxln(X)d N(X)rc2(X))A(X)[Nmax-N(X)]1/3rc(X))B(X)(12)ln A(X))const+D ln B(X)(13)Ind.Eng.Chem.Res.,Vol.36,No.5,19971599volume encompassed by the fractal surface remains unchanged in the process can eq 3be rewritten asfrom which eq 5was obtained.But the capillary condensation process cannot satisfy this condition.With the increase of the relative pressure of nitrogen,the volume encompassed by the liquid -gas interface is decreased,so Neimark’s simulation results cannot characterize the real structure of the porous media.However,when the relative pressure of nitrogen X )P/P 0is relatively small,the volume does not change remarkably,so Neimark’s relation shows seemingly reasonable results in this range.In the range of greater relative pressure of nitrogen,especially after the valueof X surpassed 0.8,the volume encompassed by the liquid -gas interface decreased remarkably with an increase of X ,so the experimental data violated the simulated straight line.Neimark cannot find the defects in his scaling law and get to the wrong conclu-sion that the scaling interval for these porous solid is very narrow.So,it is necessary that the scaling relation developed to measure the surface fractal dimension using the capillary condensation data not only conform to the theory of fractal geometry itself but also consort with the concrete process of capillary condensation as well.Obviously,this idea has been considered when the scaling relation of this paper is being deduced.By contrast,the surface fractal dimensions deter-mined by the adsorption data are smaller than those determined by the desorption data;this cannot be thought of as caused by the experimental probable error.The surface morphology is not the only factor that affects the desorption process;the topology of the porous space has a significant influence on this process.In the process of desorption,due to the “shielding”effect of the small pores on the large one,the calculating results of S E (X )are larger than those of S E in reality and thus make the discrepancy between D abs and D des .The quantitative difference between the two indicates the degree of the influence of the shielding effect,so it reflects the topological feature of the porous solid in some degree.Jaroniec (1995)compared the fractal FHH equation (3)and Neimark’s relation (5)and concluded that the two methods are theoretically equivalent.So,the FHH equation meets the same difficulty when being used to evaluate the surface fractal dimension.Sahouli et al.(1996)reexamined the two methods and concluded that the FHH type equation is also sensitive to the mi-croporous structures in contrast to Neimark’s relation,and this causes the disagreement of the results of the two methods for the solids with high surface area.In fact,the disagreement is due to the fact that the two methods were used in two different scale ranges.When being used in the same scale range,these two methods should yield the same results.The method in this work is based on the thermody-namic principle;another thermodynamic method to measure the surface fractal dimensions for the porous materials has been developed by Zhang and Li (1995).These two methods use different experimental data,with Zhang’s method using the mercury porosimetry data and the method in this work developed to use the capillary condensation data,but both are based on the same principle.In order to make a comparison between the two methods,we have done the experiments to get the mercury porosimetry and nitrogen adsorption iso-therm of the same four porous materials.The experi-mental data of mercury porosimetry are measured by means of a J5-70porosimeter made in Shanghai,People’s Republic of China.The range of pressureinFigure 1.Simulation results from eq 13for SiO 2(A).Figure 2.Simulation results from eq 5for SiO 2(A).Table 1.Surface Fractal Dimensions Determined from Equations 13and 5,Respectively,with Capillary Condensation Data in the Literature (Neimark et al.,1994)eq 13eq 5analyzed sample D des D abs a min (nm)a max (nm)D des D abs a min (nm)a max (nm)porous glass 2.52 2.35 1.089.0 2.10 2.14 1.016.0Si300 2.48 2.34 1.553.7 2.20 2.22 1.510.0MgO(A) 2.41 2.33 1.389.0 2.36 2.43 1.422.4cement 2.68 2.63 1.825.1 2.43 2.43 1.87.2MgO(B) 2.51 2.33 1.2251.0 2.54 2.55 2.713.2SiO 2(A) 2.53 2.41 1.5125.0 2.47 2.59 1.512.5O 22.67 2.65 1.179.4 2.76 2.71 1.1 5.5SiO 2(B)2.552.501.139.828.52.882.08.0S E (δ)∼δ2-D1600Ind.Eng.Chem.Res.,Vol.36,No.5,1997the experiment is from0.1to300MPa.The experi-mental data of the nitrogen adsorption isotherm are measured by means of a CHEMBET-3000adsorption apparatus made by Quantachrome Co.,Syosset,NY. The simulation results are demonstrated in Table2. The simulation results show that the surface fractal dimensions determined by mercury porosimetry,D m,are larger than both D abs and D des.In the process of adsorption,before capillary condensation occurs,there has been a nitrogen film adsorbed on the surface of the porous solid.As a result,the interface between the film and the vapor,with which the film is in equilibrium,is no longer a simple replica of the film-solid interface. Due to the effect of the surface tension,the D abs is smaller than the real dimension of the fractal surface. So,the discrepancy between D abs and D real is determined by the competition between the attractive van der Waals gas-solid potential and the repulsive surface free energy of the nitrogen film.The potential wants to make the film-vapor interface follow the ups and downs of the surface as closely as possible,so that the adsorbed molecules get to set as close to the solid surface as possible.The surface tension,on the other hand,wants to make the film-vapor interface as flat as possible,so as to minimize the surface area of the interface;the two effects entangled together make the discrepancy be-tween D abs and D real.These effects,also,act on the determination of D des.On the other hand,the shielding effect makes the surface fractal dimension D m deter-mined by mercury porosimetry larger than the real dimension of the fractal surface,so it is not surprising that D m ofγ-Al2O3(C)is greater than 3.So,the shielding effect of the small pores on the large one and the effect of the surface tension result in D m>D des> D abs,which is proved by this work.From the analysis above,we can see that the discrepancies between D m and D real,D des and D abs show the shielding effect of the small pores on the large one,while the discrepancies between D real and D abs,D m and D des show the effect of the surface tension.So,we can easily get the conclusion that the following relation exists:The real surface fractal dimension of porous media can be determined by D abs,D des,and D m jointly. ConclusionA new method is proposed to determine the surface fractal dimension for a porous solid.The method is based on the approximation of a given fractal surface by inscribed equicurvature surfaces of varying mean curvature radius.The practical realization of this method for determining the surface fractal dimension of real porous materials is provided by analyzing experimental data of capillary condensation.The simulations for several kinds of porous media are fulfilled by analyzing the nitrogen adsorption isotherm and mercury porosimetry from the literature and our own.The results show that D abs,D des,and D m are different and D m>D des>D abs.By analyzing the process of adsorption,desorption of nitrogen,and mer-cury incursion,the author gives a reasonable explana-tion of the results and achieves the conclusion that D real )D abs+(D m-D des))D m-(D des-D abs).So,the real surface fractal dimension cannot be determined by D abs, D des,and D m,respectively,but jointly. AcknowledgmentSupport from funds of Science and Technology of National Education Committee of People’s Republic of China is gratefully acknowledged.Nomenclaturea min)outer cutoff of a finite scaling regimea max)inner cutoff of a finite scaling regimeD)fractal dimension of pore surfacek0)shape factorN)physisorption quantity,molP)current pressure of nitrogen,PaP0)saturation pressure of nitrogen,Par c)mean curvature radius,mS E)fractal area of pore surface in Euclidean space,m2 T)absolute temperature of the adsorption,KV)volume of the space encompassed by the fractal surface,m3V L)molar volume of liquid nitrogen,m3/molGreek Symbolsδ)yardstick size of measurements,mµ)chemical potential energy,J/molσ)surface tension between liquid and gas of nitrogen,J/m Literature CitedAubert,C.;Cannel,D.S.Restructuring of Colloidal Silica Ag-gregates.Phys.Rev.Lett.1986,56,738.Avnir,D.;et al.A Discussion of Some Aspects of Surface Fractality and Its Determination.New J.Chem.1992,16(4),439. Freltoft,T.;et al.Power-law Correlations and Finite-size Effects in Silica Particle Aggregates Studied by Small-angle Neutron Scattering.Phys.Rev.B1986,33(1),269.Jaroniec,M.Evaluation of the Fractal Dimension From a Single Adsorption ngmuir1995,11,2316.Jaroniec,M.;Madey,R.Physical Adsorption on Heterogeneous Solids;Elsevier:Amsterdam,The Netherlands,1988. Mandelbrot,B.B.The Fractal Geometry of Nature;Freeman:New York,1982;p109.Martin,J.E.;et al.Fractal Geometry of Vapor-phase Aggregates.Phys.Rev.A1986,33(5),3540.Table2.Surface Fractal Dimension Determined from Equation13and Zhang’s Relationeq13Zhang’s relation analyzedsample D abs D des a min(nm)a max(nm)D m a min(nm)a max(nm)γ-Al2O3(A) 2.75 1.024.0 2.81 2.025.7 B106 2.72 1.024.0 2.80 2.025.7γ-Al2O3(B) 2.68 1.024.0 2.72 2.025.7γ-Al2O3(C) 2.66 2.75 1.024.0 3.07 2.026.3Dreal )Dabs+(Dm-Ddes))Dm-(Ddes-Dabs)Ind.Eng.Chem.Res.,Vol.36,No.5,19971601Neimark,A.V.A New Approach to the Determination of the Surface Fractal Dimension of Porous Solids.Physica A1992, 191,258.Neimark,A.V.;et al.Determination of the Fractal Dimension for Porous Solids from Adsorption Isotherm of Nitrogen.Z.Phys.Chem.1994,187,265.Pfeifer,P.Structure analysis of Porous Solids From Presorbed ngmuir1991,7,2833.Pfeifer,P.;Avnir,D.Chemistry in Noninteger Dimensions Be-tween Two and Three.J.Chem.Phys.1983,79(7),3558. Pfeifer,P.;Cole,M.W.Fractals in Surface Science:Scattering and Thermodynamics of Adsorbed Films II.New J.Chem.1990,14,221.Zhang,B.;Li,S.Determination of the Surface Fractal Dimension for Porous Media by Mercury Porosimetry.Ind.Eng.Chem.Res.1995,34,1383.Received for review September9,1996 Revised manuscript received January27,1997Accepted February3,1997XIE960555W X Abstract published in Advance ACS Abstracts,March15, 1997.1602Ind.Eng.Chem.Res.,Vol.36,No.5,1997。
药学英语第五版原文翻译
Introduction to PhysiologyIntroductionPhysiology is the study of the functions of living matter. It is concerned with how an organism performs its varied activities: how it feeds, how it moves, how it adapts to changing circumstances, how it spawns new generations. The subject is vast and embraces the whole of life. The success of physiology in explaining how organisms perform their daily tasks is based on the notion that they are intricate and exquisite machines whose operation is governed by the laws of physics and chemistry.Although some processes are similar across the whole spectrum of biology—the replication of the genetic code for or example—many are specific to particular groups of organisms. For this reason it is necessary to divide the subject into various parts such as bacterial physiology, plant physiology, and animal physiology.To study how an animal works it is first necessary to know how it is built. A full appreciation of the physiology of an organism must therefore be based on a sound knowledge of its anatomy. Experiments can then be carried out to establish how particular parts perform their functions. Although there have been many important physiological investigations on human volunteers, the need for precise control over the experimental conditions has meant that much of our present physiological knowledge has been derived from studies on other animals such as frogs, rabbits, cats, and dogs. When it is clear that a specific physiological process has a common basis in a wide variety of animal species, it is reasonable to assume that the same principles will apply to humans. The knowledge gained from this approach has given us a great insight into human physiology and endowed us with a solid foundation for the effective treatment of many diseases.The building blocks of the body are the cells, which are grouped together to form tissues. The principal types of tissue are epithelial, connective, nervous, and muscular, each with its own characteristics. Many connective tissues have relatively few cells but have an extensive extracellular matrix. In contrast, smooth muscle consists of densely packed layers of muscle cells linked together via specific cell junctions. Organs such as the brain, the heart, the lungs, the intestines, and the liver are formed by the aggregation of different kinds of tissues. The organs are themselves parts of distinct physiological systems. The heart and blood vessels form the cardiovascular system; the lungs, trachea, and bronchi together with the chest wall and diaphragm form the respiratory system; the skeleton and skeletal muscles form the musculoskeletal system; the brain, spinal cord, autonomic nerves and ganglia, and peripheral somatic nerves form the nervous system, and so on.Cells differ widely in form and function but they all have certain生理学简介介绍生理学是研究生物体功能的科学。
榛蘑与菌丝体中蜜环菌素的超声波辅助提取条件优化及其提取物中化合物分析
徐伟,王植朔,王瑞琦,等. 榛蘑与菌丝体中蜜环菌素的超声波辅助提取条件优化及其提取物中化合物分析[J]. 食品工业科技,2022,43(19):298−306. doi: 10.13386/j.issn1002-0306.2022050143XU Wei, WANG Zhishuo, WANG Ruiqi, et al. Optimization of Ultrasonic-assisted Extraction Conditions of Melleolides from Wild Armillaria mellea and Liquid Culture Mycelium, and Analysis of Their Compounds in Extracts[J]. Science and Technology of Food Industry, 2022, 43(19): 298−306. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2022050143· 工艺技术 ·榛蘑与菌丝体中蜜环菌素的超声波辅助提取条件优化及其提取物中化合物分析徐 伟,王植朔,王瑞琦,吴 凡,梁珊珊,谢红瑶,张 雪(哈尔滨商业大学食品工程学院,黑龙江哈尔滨 150028)摘 要:目的:为分析榛蘑与菌丝体中化合物差异,本研究以东北野生榛蘑子实体和液态菌丝体为研究对象,探究蜜环菌素的最佳提取工艺条件,并对提取物中化合物进行分析。
方法:以提取物得率和蜜环菌素含量为指标,采用超声波细胞破碎辅助石油醚进行萃取,通过单因素实验和正交试验对提取工艺参数进行优化;采用超高效液相色谱-串联质谱(UHPLC-MS/MS )技术,对液态菌丝体和榛蘑子实体中化合物进行分析和鉴定。
结果:确定最佳提取工艺条件为料液比1:20 g/mL ,超声波功率300 W ,超声时间20 min ,溶剂回流时间50 min ,在该条件下液态菌丝体提取物得率为26.8%,蜜环菌素含量为0.74 mg/g ;液态菌丝体和榛蘑子实体中化合物分别为305和592个。
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a r X i v :h e p -p h /0612094v 2 31 A u g 2007Drell-Yan processes,transversity and light-cone wavefunctionsB.Pasquini,M.Pincetti,S.BoffiDipartimento di Fisica Nucleare e Teorica,Universit`a degli Studi di Pavia and INFN,Sezione di Pavia,Pavia,Italy(Dated:February 2,2008)The unpolarized,helicity and transversity distributions of quarks in the proton are calculated in the overlap representation of light-cone wavefunctions truncated to the lowest order Fock-space components with three valence quarks.The three distributions at the hadronic scale satisfy an interesting relation consistent with the Soffer inequality.Results are derived in a relativistic quark model including evolution up to the next-to-leading order.Predictions for the double transverse-spin asymmetry in Drell-Yan dilepton production initiated by proton-antiproton collisions are presented.Asymmetries of about 20–30%are found in the kinematic conditions of the PAX experiment.PACS numbers:13.88.+e.Hb,13.85.Qk,12.39.Ki I.INTRODUCTIONAt the parton level the quark structure of the nucleon is described in terms of three quark distributions,namely the quark density f 1(x ),the helicity distribution g 1(x )(also indicated ∆f (x )),and the transversity distribution h 1(x )(also indicated δf (x )).The first two distri-butions,and particularly f 1(x ),are now well established by experiments in the deep-inelastic scattering (DIS)regime and well understood theoretically as a function of the fraction x of the nucleon longitudinal momentum carried by the active quark [1].Information on the last leading-twist distribution is missing on the experimental side because h 1(x ),being chiral odd,decouples from inclusive DIS and therefore can not be measured in such a traditional source of information.Nevertheless some theoretical activity has been developed in calcu-lating h 1(x )and finding new experimental situations where it can be observed (for a recent review see Ref.[2]).Among the different proposals the polarized Drell-Yan (DY)dilepton production was recognized for a long time as the cleanest way to access the transversity dis-tribution of quarks in hadrons[3,4,5,6].As a matter of fact,in pp and p¯p DY collisions with transversely polarized hadrons the leading order(LO)double transverse-spin asymmetry of lepton-pair production involves the product of two transversity distributions,thus giving direct access to them.However,such a measurement is not an easy task because of the tech-nical problems of maintaining the beam polarization through the acceleration.The recently proposed experimental programs at RHIC[7]and at GSI[8]have raised renewed interest in theoretical predictions of the double transverse-spin asymmetry in proton-(anti)proton collisions with dilepton production[9,10,11].As reviewed in[2],h1(x)has been calculated in a variety of models,including relativistic bag-like,chiral soliton,light-cone,and spectator models.In all these calculations the an-tiquark transversity is rather small and the d-quark distribution turns out to have a much smaller size than the u-quark distribution.In this paper h1(x)and the other quark distributions are derived within the framework of the overlap representation of light-cone wavefunctions(LCWFs)originally proposed in Refs.[12]to construct generalized parton distributions(GPDs).A Fock-state decomposi-tion of the hadronic state is performed in terms of N-parton Fock states with coefficients representing the momentum LCWF of the N partons.Direct calculation of LCWFs from first principles is a difficult task.On the other hand,constituent quark models(CQMs) have been quite successful in describing the spectrum of hadrons and their low-energy dy-namics.At least in the kinematic range where only quark degrees of freedom are effective, it is possible to assume that at the low-energy scale valence quarks can be interpreted as the constituent quarks treated in CQMs.In the region where they describe emission and reabsorption of a single active quark by the target nucleon,quark GPDs are thus linked to the non-diagonal one-body density matrix in momentum space and can be calculated both in the chiral-even and chiral-odd sector[13,14,15].Sea effects represented by the meson cloud can also be integrated into the valence-quark contribution to GPDs[16].In such an approach the quark distributions,being the forward limit of GPDs,are related to the diagonal part of the one-body density matrix in momentum space.The paper is organized as follows.In Sect.II the overlap representation of LCWFs is briefly reviewed with the aim of linking the parton distributions to CQMs.Results for the three valence quark distributions are discussed at the hadronic scale and after evolution up to the next-to-leading(NLO)in Sect.III.The application to double transverse-spinasymmetry in DY collisions is presented in Sect.IV,andsomeconclusions are drawn in the final Section.II.THE OVERLAP REPRESENTATION FOR PARTON DISTRIBUTIONSIn the overlap representation of LCWFs[12]the proton wave function with four-momentum p and helicityλis expanded in terms of N-parton Fock-space components, i.e.|p,λ = N,β [d x]N[d2 k⊥]NΨ[f]λ,N,β(r)|N,β;k1,...,k N ,(1) whereΨ[f]λ,N,βis the momentum LCWF of the N-parton Fock state|N,β;k1,...,k N .The integration measures in Eq.(1)are defined as[d x]N=Ni=1dx iδ 1−N i=1x i ,[d2 k⊥]N=1M0ω1ω2ω32,and the matrices D1/2µiλi(R cf(k i))are given by the spin-space representation of the Melosh rotation R cf,D1/2λµ(R cf(k))= λ|R cf(xM0, k⊥)|µ= λ|m+xM0−i σ·(ˆ z× k⊥)(m+xM0)2+ k2⊥|µ .(4)In this approach the ordinary(unpolarized)parton distributions offlavor q[17]can be recovered taking into account that in this case the Melosh rotation matrices combine to the identity matrix:f q1(x)= λiτi3 j=1δτjτq [dx]3[d k⊥]3δ(x−x j)|Ψ[f]λ({x i},{ k⊥,i};{λi},{τi})|2,(5) where the helicityλof the nucleon can equivalently be taken positive or negative.Analo-gously,the following simple expressions are obtained for the polarized quark distribution of flavor q[14]g q1(x)= λiτi3 j=1δτjτq sign(λj) [dx]3[d k⊥]3δ(x−x j)|Ψ[f]+({x i},{ k⊥,i};{λi},{τi})|2,(6) and for the quark transversity distributions h q1(x)[15]:h q1(x)= λt iτi3 j=1δτjτq sign(λt j) [dx]3[d k⊥]3δ(x−x j)|Ψ[f]↑({x i},{ k⊥,i};{λt i},{τi})|2,(7) whereλt i is the transverse-spin component of the quark and,as usual,the transversity basis for the nucleon spin states is obtained from the helicity basis as follows:|p,↑ =12(|p,+ +|p,− ),|p,↓ =12(|p,+ −|p,− ).(8) Expressions(5),(6)and(7)exhibit the well known probabilistic content of parton distri-butions.Eq.(5)gives the probability offinding a quark with a fraction x of the longitudinal momentum of the parent nucleon,irrespective of its spin orientation.The helicity distri-bution g q1(x)in Eq.(6)is the number density of quarks with helicity+minus the number density of quarks with helicity−,assuming the parent nucleon to have helicity+.The transversity distribution h q1(x)in Eq.(7)is the number density of quarks with transverse polarization↑minus the number density of quarks with transverse polarization↓,assuming the parent nucleon to have transverse polarization↑.In the instant form it is convenient to separate the spin-isospin component from the space part of the proton wave function and to assume SU(6)symmetry,i.e.Ψ[c]λ({ k i},{λi},{τi})=ψ( k1, k2, k3)Φλτ(λ1,λ2,λ3,τ1,τ2,τ3),(9) whereΦλτ(λ1,λ2,λ3,τ1,τ2,τ3)=12 Φ0λ(λ1,λ2,λ3)Φ0τ(τ1,τ2,τ3)+Φ1λ(λ1,λ2,λ3)Φ1τ(τ1,τ2,τ3),(10)with the superscripts0and1referring to the total spin or isospin of the pair of quarks1 and2.Thus wefindf q1(x)= 2δτq1/2+δτq−1/2 [dx]3[d k⊥]3δ(x−x3)|ψ({x i},{ k⊥,i})|2,(11)g q1(x)= 43δτq−1/2 [dx]3[d k⊥]3δ(x−x3)|ψ({x i},{ k⊥,i})|2M,(12)h q1(x)= 43δτq−1/2 [dx]3[d k⊥]3δ(x−x3)|ψ({x i},{ k⊥,i})|2M T,(13) where[15,18]M=(m+x3M0)2− k2⊥,3(m+x3M0)2+ k2⊥,3,(15) and the expectation values on the normalized nucleon momentum wavefunction of the con-tribution coming from Melosh rotations satisfy2 M T = M +1.(16) Therefore the following relations holdh u1(x)=13f u1(x),h d1(x)=16f d1(x),(17)which are compatible with the Soffer inequality[19]:|h q1(x)|≤13f u1and h d1=g d1=−1axial-vector coupling constant G A and giving also a good agreement with the experimental nucleon electroweak form factors in a large Q2range.Furthermore,we note that SU(6) symmetry is broken in the LCWFΨ[f][21]as a consequence of the transformation(3).The distributions in Eqs.(11),(12)and(13)are defined at the hadronic scale Q20of the model.In order to make predictions for experiments,a complete knowledge of the evolution up to NLO is indispensable.According to Ref.[22]we assume that twist-two matrix elements calculated at some low scale in a quark model can be used in conjunction with QCD perturbation theory.Starting from a scale where the long-range(confining)part of the interaction is dominant,we generate the perturbative contribution by evolution at higher scale.In the case of transversity the Dokshitzer-Gribov-Lipatov-Altarelli-Parisi(DGLAP) Q2evolution equation[23]is simple.In fact,being chirally odd,the quark transversity distributions do not mix with the gluon distribution and therefore the evolution is of the non-singlet type.The leading order(LO)anomalous dimensions werefirst calculated in Ref.[24]but promptly forgotten.They were recalculated by Artru and Mekhfi[25].The one-loop coefficient functions for Drell-Yan processes are known in different renormalization schemes[26,27,28].The NLO(two-loop)anomalous dimensions were also calculated in the Feynman gauge in Refs.[29,30]and in the light-cone gauge[31].The two-loop splitting functions for the evolution of the transversity distribution were calculated in Ref.[31].The LO DGLAP Q2evolution equation for the transversity distribution h1(x)was derived in Ref.[25]and its numerical analysis is discussed in Refs.[32,33].A numerical solution of the DGLAP equation for the transversity distribution h1(x)was given at LO and NLO in Refs.[34,35].In Ref.[34]the DGLAP integrodifferential equation is solved in the variable Q2with the Euler method replacing the Simpson method previously used in the cases of unpolarized[36]and longitudinally polarized[37]structure functions.In the present analysis the FORTRAN code of Ref.[34]has been applied within thecode at NLO is computed by solving the NLO transcendental equation numerically,ln Q2β0αs+β1β0αs+β14π=1β20ln ln(Q2/Λ2NLO)0.20.40.60.8100.20.40.60.81x f 1u 00.20.40.60.8100.20.40.60.81x f 1d 00.511.500.20.40.60.81NS x x f 1u 00.20.40.60.8100.20.40.60.81NS x x f 1d Figure 1:Evolution of the parton distribution for the u (left panel)and d (right panel)quark.Inthe lower panels starting from the hadronic scale Q 20=0.079GeV 2(upper curve),LO non-singletdistributions are shown at different scales (Q 2=5GeV 2,solid lines;Q 2=9GeV 2,dashed lines;Q 2=16GeV 2,dotted lines)together with NLO distributions at Q 2=5GeV 2(dot-dashed lines).LO and NLO total distributions are shown in the upper panels with the same line convention.The parametrization of Ref.[39]NLO evolved at 5GeV 2is also shown by small stars.In any case the Soffer inequality (18)at each order is always satisfied by the three quark distributions calculated with the LCWFs of the present model (see Fig.4).In contrast,saturation of the Soffer bound,i.e.assuming|h q 1(x )|=100.20.400.20.40.60.81 x x g 1u -0.05000.20.40.60.81x x g 1d 00.5100.20.40.60.81NS x x g 1u -0.2-0.1000.20.40.60.81NSx x g 1d Figure 2:The same as in Fig.1,but for the helicity distribution.evolution.In fact,starting at the hadronic scale with the transversity distribution given by Eq.(21),the result of LO and NLO evolution diverges from that obtained when calculating the transversity according to Eq.(21)after separate evolution of f 1and g 1.Since the two sides of Eq.(21)give different results under evolution,in model calculations the choice of the initial hadronic scale is crucial.This fact should put some caution about the possibility of making predictions with the transversity distribution guessed from f 1and g 1as,e.g.,in the case of the double transverse-spin asymmetry in DY processes (see Refs.[10,11]and Fig.7below).A similar situation occurs when the transversity distribution is derived from f 1and g 1according to the relations (17),with the difference that these relations are exact at the hadronic scale when only valence quarks are involved.00.20.40.60.8100.250.50.751NS x x h 1u-0.3-0.2-0.1000.250.50.751NS x x h 1d Figure 3:Evolution of the transversity distribution for the u (left panel)and d (right panel)quark.Starting from the hadronic scale Q 20=0.079GeV 2(upper curve),LO non-singlet distributions areshown at different scales (Q 2=5GeV 2,solid lines;Q 2=9GeV 2,dashed lines;Q 2=16GeV 2,dotted lines)together with NLO distributions at Q 2=5GeV 2(dot-dashed lines).IV.THE DOUBLE TRANSVERSE-SPIN ASYMMETRYIn order to directly access transversity via Drell-Yan lepton pair production one has to measure the double transverse-spin asymmetry A T T in collisions between two transversely polarized hadrons:A T T =dσ↑↑−dσ↑↓q e 2q f q 1(x 1,Q 2)f ¯q 1(x 2,Q 2)+(1↔2) ,(23)where e q is the quark charge,Q 2the invariant mass square of the lepton pair (dimuon),and00.511.500.250.50.751NS x x h 1u -0.3-0.2-0.1000.250.50.751NSx x h 1d Figure 4:The transversity distribution obtained with the LCWFs of the present model (thin lines)compared with the Soffer bound,Eq.(21),(thick lines)for the u (left panel)and d (right panel)quark .Solid lines for the results at the hadronic scale Q 20=0.079GeV 2,the dashed lines obtainedby NLO evolution at Q 2=9GeV 2,respectively.x 1x 2=Q 2/s where s is the Mandelstam variable.The quantity a T T is the spin asymmetry of the QED elementary process q ¯q →ℓ+ℓ−,i.e.a T T (θ,φ)=sin 2θat RHIC very small,no more than a few percents[33,42,45].A more favorable situation is expected by using an antiproton beam instead of a proton beam[8,9,10,11,46].In p¯p DY the LO asymmetry A p¯p T T is proportional to a product of quark transversity distributions from the proton and antiquark distributions from the antiproton which are connected by charge conjugation,e.g.h u/p 1(x)=h¯u/¯p1(x).(25)Therefore one obtainsA p¯p T T=a T Tq e2q h q1(x1,Q2)h q1(x2,Q2)+h¯q1(x1,Q2)h¯q1(x2,Q2)2lnx10.10.20.30.40.500.20.40.60.81 1.2yA T T /a T T Figure 5:The double transverse-spin asymmetry A p ¯p T T /a T T calculated with the parton distributionsof the present model as a function of the rapidity y at different scales:Q 2=5GeV 2,solid line;Q 2=9GeV 2,dashed line;Q 2=16GeV 2,dotted line.This result confirms the possibility of measuring the double transverse-spin asymmetry under conditions that will be probed by the proposed PAX experiment.In such conditions,assuming the LO expression (26)for the observed asymmetry one could gain direct infor-mation on the transversity distribution following previous analyses [9,10,11],where thequark densities f q,¯q 1(x,Q 2)are taken from the GRV98parametrizations [39].The resultingtransversity distributions could be compared with model predictions.According to this strategy,with the present model the antiquark distributions h ¯q 1(x,Q 2)are identically vanishing and h q 1(x,Q 2)contains only valence quark contributions.Assuminga negligible sea-quark contribution the corresponding asymmetry would thus give directaccess to h q 1(x,Q 2)and would look like that shown in Fig.6.The results indicate a strongQ 2dependence suggesting moderate values of Q 2,e.g.Q 2=5to 10GeV 2,in order to have an appreciable asymmetry of about 10–20%at the proposed PAX experiment at GSI [8].It is remarkable that,contrary to the result of Ref.[9],in the present model Q 2evolution produces a decreasing LO asymmetry with increasing Q 2as a consequence of the opposite00.10.20.300.20.40.60.81yA T T /a T T Figure 6:The same as in Fig.5but assuming the GRV98[39]quark density.00.20.400.20.40.60.81yA T T /a T T Figure 7:The double transverse-spin asymmetry A p ¯p T T /a T T as a function of the rapidity y at Q 2=5GeV 2and s =45GeV 2.Solid curve:calculation with h 1obtained with the LCWFs of the present model.Dashed curve:calculation with an input h 1=1Q2dependence of the theoretical h1and the phenomenological f1.In fact,in the range of x-values explored by the chosen kinematic conditions(x≥0.3)h1with its valence quark contribution has a larger fall-offwith Q2than the GRV98f1as shown in Fig.1.Furthermore, one may notice that with the present model a much lower asymmetry is predicted than with the chiral quark-soliton model[9]and even lower than the phenomenological analysis of Refs.[10,11].In general,one can anticipate upper and lower limits for the theoretical asymmetry depending on the upper and lower bounds that the transversity has to satisfy.The saturated Soffer bound(21),i.e.h1=1(g1+f1)(dashed curve)or assuming2the nonrelativistic approximation h1=g1(dotted curve),with f1and g1calculated in the present model.The difference between the dotted and solid curves gives an estimate of the relativistic effects in the calculation of h1.On the other side,the model calculation with an input h1satisfying Eq.(17)leads to an asymmetry much lower than in the case of the saturated Soffer bound.V.CONCLUSIONSThe unpolarized,helicity and transversity distributions of quarks in the proton are calcu-lated in the overlap representation of light-cone wavefunctions truncated to the lowest order Fock-space components with three valence quarks.The light-cone wavefunctions have been defined making use of the correct covariant connection with the instant-form wavefunctions used in any constituent quark model.The quark distributions have been evolved to leading order and next-to-leading order of the perturbative expansion with the remarkable result that NLO effects are rather small compared to LO.The three distributions at the hadronicscale satisfy an interesting relation consistent with the Soffer inequality.In particular,the transversity distribution has been used to predict the double transverse-spin asymmetry in dilepton production with Drell-Yan collisions between transversely polarized beams of protons and antiprotons.As a function of rapidity the asymmetry calculated in the model is about30%for s=45GeV2,slightly increasing with Q2.In contrast,when using phe-nomenological unpolarized quark distributions together with the transversity distribution derived in the present model,the asymmetry turns out to be smaller than previous predic-tions,e.g.about10–20%at Q2=5GeV2and s=45GeV2,and rapidly decreases with increasing Q2.This is due to the different Q2dependence of the involved distributions in the allowed range of x values.As the transversity is unknown experimentally,this sensitivity to Q2is an important argument for future experiments.The present results suggest the possibility of measurable asymmetries at moderate values of Q2in the kinematic conditions of the proposed PAX experiment,thus obtaining direct access to the quark transversity 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