Direct synthesis of isoparaffin by modified Fischer–Tropsch synthesis using hybrid catalyst of iron
Designing a Capsule Catalyst and Its Application for Direct Synthesis of Middle Isoparaffins
Designing a Capsule Catalyst and Its Application forDirect Synthesis of Middle IsoparaffinsJingjiang He,†Yoshiharu Yoneyama,†Bolian Xu,‡Norikazu Nishiyama,§andNoritatsu Tsubaki*,†Department of Applied Chemistry,School of Engineering,Toyama University,Gofuku 3190,Toyama 930-8555,Japan,Department of Chemistry,Nanjing University,Nanjing 210093,China,and Division of Chemical Engineering,Graduate School of Engineering Science,OsakaUniversity,Osaka 560-8531,JapanReceived November 12,2004.In Final Form:January 12,2005A catalyst in the form of a capsule catalyst was prepared by coating HZSM5membrane on a preshaped Co/SiO 2catalyst pellet.The capsule catalyst with HZSM5membrane exhibited excellent selectivity for light hydrocarbon synthesis,especially for isoparaffin synthesis from syngas (CO +H 2).Long-chain hydrocarbon formation was totally suppressed by the zeolite membrane.The modification of membrane and core catalyst significantly improved the catalytic properties of these new kinds of capsule catalysts.IntroductionThe Fischer -Tropsch synthesis (FTS)reaction,CO +H 2)hydrocarbons +H 2O,was found by Fischer and Tropsch in 1925.1It can produce liquid fuels such as gasoline and diesel oil from coal or natural gas.As more and more natural gas resources are found in the world presently,the FTS process becomes more promising.2Furthermore,as the technique of producing syngas (CO +H 2)from biomass is being developed,synthetic liquid fuel can be obtained from biomass via FTS.3The FTS products are almost normal hydrocarbons,either olefins or paraffins,and the product selectivity follows the ASF distribution.The advantages of FTS hydrocarbons are their high n -paraffin content,high cetane number as diesel fuel,and sulfur-free,aroma-free,nitrogen-free properties,especially on cobalt-based catalysts.4-7The production of hydrocarbons rich in isoparaffins,alkylates,has gained much attention because of its high octane numbers if used as synthetic gasoline.Several groups have tried to make isoparaffins by utilizing FTS catalyst,which is metal dispersed on acidic zeolite or other acidic supports.8But these catalysts performed with very low conversion due to a rather low reduction degree.We have recently reported that when a mechanical mixture of zeolite and normal FTS catalyst,Co/SiO 2,was used in a single-or dual-step FTS reaction,the formation of short-chain isoparaffins was enhanced while the formation of longer hydrocarbons was suppressed.9Zeolite is a special material with unique pores and channels.The varied molecular diffusion rate in these pores and the shape selectivity,as well as acidic properties,make it widely used.Many studies on preparing zeolite membrane and its application for separation have already been reported.10On the other hand,zeolite is also a good hydrocracking/hydroisomerization catalyst due to its acidic properties.11In the present work,zeolite membrane was tailor-made coated on the FTS catalyst pellet,Co/SiO 2,and we call it a capsule catalyst.In the reaction,feed gas,CO +H 2,diffused through zeolite membrane and arrived at the FTS catalyst.Then the hydrocarbons formed there and desorbed.When the hydrocarbons diffused into the zeolite membrane,all of them,in the form of normal hydrocarbons,could enter zeolite channels and must be cracked and isomerized by acidic sites inside zeolite channels.A schematic image is shown in Figure 1.For long-chain hydrocarbons,their low diffusion rate in zeolite membrane makes them stay in the membrane layer longer,having a higher possibility of isomerization and cracking reaction inside the membrane.Furthermore,compared to conventional membrane reactors,the catalyst designed above has larger membrane area per unit reactor volume.This kind of capsule catalyst is of great advantage in practical application,because membranes with large area and without pinholes or cracks are very difficult to*To whom correspondence should be addressed.E-mail:tsubaki@eng.toyama-u.ac.jp.†Toyama University.‡Nanjing University.§Osaka University.(1)Olive,H.G.;Olive,S.The Chemistry of the Catalyzed Hydrogena-tion of Carbon Monoxide ;Springer-Verlag:Tokyo,1984;p 144.(2)Wegrzyn,J.E.;Mahajan,D.;Gurevich,M.Catal.Today 1999,50,97.(3)Chum,H.L.R.;Overend,P.Fuel Process.Technol.2001,71,187.(4)Iglesia,E.;Soled,S.L.;Fiato,R.A.J.Catal .1992,137,212.(5)Johnson,B.G.;Bartholomew,C.H.;Goodman,D.W.J.Catal .1991,128,231.(6)Schanke,D.;Vada,S.;Blekkan,E.A.;Hilman,A.M.;Hoff,A.;Holmen,A.J.Catal .1995,156,85.(7)Van Der Laan,G.P.;Beenackers,A.Catal.Rev.Sci.Eng.1999,41,255.(8)Chen,Y.W.;H.T.Tang;Goodwin,J.G.,Jr.J.Catal .1983,83,415.Nijs,H.H.;Jacobs,P.A.J.Catal .1980,66,401.Jacobs,P.A.Catalysis by Zeolites ;Imelik,B.,Naccache,C.,Vedrine,J.C.,Eds.;Elsevier:Amsterdam,1980;p 293.(9)Li,X.;Asami,K.;Luo,M.;Michiki,K.;Tsubaki,N.;Fujimoto,K.Catal.Today 2003,84,59.(10)de Vos,R.M.;Verweij,H.Science 1998,279,1710.Nishiyama,N.;Miyamoto,M.;Egashira,Y.;Ueyama,mun.2001,18,i,Z.;Bonlla,G.;Diaz,I.;Nery,J.G.;Sujaoti,K.;Amat,M.A.;Kokkoli,E.;Terasaki,O.;Thompson,R.W.;Tsapatsis,M.D.;Vlachos,G.Science 2003,300,456.(11)Feller,A.;Guzman,A.;Zuazo,I.;Lercher,J.A.J.Catal.2004,224,80.Figure 1.A schematic image of the capsule catalyst role in the FTS reaction.1699Langmuir 2005,21,1699-170210.1021/la047217h CCC:$30.25©2005American Chemical SocietyPublished on Web 02/01/2005prepare in most cases.12This new kind of capsule catalyst is expected to have wide applications,if the combination of core catalyst and membrane catalyst is varied according to the target reaction.Experimental SectionThe conventional FTS catalyst was prepared by incipient-wetness impregnation of an aqueous solution of Co(NO 3)2‚6H 2O and two kinds of silica support (Cariact Q-10,Fuji Silysia Co.;specific surface area,323m 2‚g -1;pore volume,1.03mL ‚g -1;pore diameter,10nm)whose pellet size was 0.85-1.7and 0.38-0.50mm,respectively.The catalyst precursors were dried in air at 393K for 12h and then calcined in air from room temperature to 673K with a ramping rate of 2K ‚min -1and kept at 673K for 2h.After calcination,the catalysts were cooled to room temperature in nitrogen.In zeolite membrane synthesis,distilled water and ethanol (Wako Pure Chemical Industries Ltd.,99.5%)were used for solutions.The templet was TPAOH (tetrapropylammonium hydroxide solution,Wako Pure Chemical Industries Ltd).Al and Si sources were Al(NO 3)3‚9H 2O (99.5%)and TEOS (tetraethyl ortho silicate;Wako Pure Chemical Industries Ltd.),respectively.TEOS/TPAOH/H 2O/EtOH/Al(NO 3)3)1:0.25:60:4:0.025.First,TEOS,10%TPAOH water solution,ethanol,and water were added in a 100mL Teflon tank.Then Al(NO 3)3‚9H 2O was added to the mixture solution carefully and stirred at 333K for 2h until the lucid sol was formed.Continuously,the normal FTS catalyst was added in the sol,and the capped tank was put in hydrothermal synthesis equipment (DRM-420DA,Hiro Co.,Japan),heated to 453K,and run at 10rpm with various duration times for crystallization.In this process,the zeolite membrane was coated on the surface of FTS catalyst pellets.Then,the coated catalyst was separated from the synthesis solution and dried at 393K for 12h,followed by calcination at 773K for 5h where the temperature rising rate was 1K/min from 393to 773K.Thus,a capsule catalyst was obtained.The pure zeolite wassynthesized by the same method without adding the Co/SiO 2catalyst,as a blank experiment.The morphology and surface component analysis of the Co/SiO 2catalyst and the prepared capsule catalysts were investi-gated with a scanning electron microscope equipped with an EDX attachment (JEOL JSM-6360LV,15-20kV,1.0nA).The catalyst was precoated with Pt before characterization.The FTS reaction was conducted under pressurized conditions,1.0MPa,533K,by using a flow-type fixed reactor.Before reaction,the catalyst was reduced in flowing hydrogen at 80mL/min at 673K for 10h and at last cooled to 353K in nitrogen.The catalyst amount was 0.5g on the Co/SiO 2base,and the H 2/CO ratio of the feed gas was 2.During the reaction,effluent gas released from the reactor was analyzed by on-line gas chromatography using an active charcoal column equipped with a thermal conductivity detector (TCD).The hydrocarbons were also ana-lyzed on-line using a capillary column (J&W Scientific GS-Alumina,30m)equipped with a hydrogen flame ionization detector (FID).A trap with concentrated sulfuric acid was attached to the system for adsorbing the olefins.The olefin hydrocarbons were calculated from difference of FID peaks after the olefins were absorbed by the concentrated sulfuric acid.Results and DiscussionThe morphology of the Co/SiO 2FTS catalyst and the obtained capsule catalysts is shown in Figure 2.The image of a capsule catalyst in Figure 2B suggested that the HZSM5crystal formed on the surface of the Co/SiO 2catalyst pellet,while no crystals were observed on the Co/SiO 2pellet surface as in Figure 2A.The EDS plane analysis results confirmed the formation of zeolite mem-brane on the Co/SiO 2pellet because there was Al X-ray signal on the capsule catalysts but not on the Co/SiO 2catalyst as shown in Figure 2C,D.Furthermore,no cobalt was detected on the capsule catalyst,indicating the zeolite membrane was perfect.Figure 3shows a cross-sectional view of the prepared capsule catalyst pellet.The zeolite membrane can be clearly distinguished from the cobalt(12)Nishiyama,N.;Ichioka,K.;Park,D.H.;Egashira,Y.;Ueyama,K.;Gora,L.;Zhu,W.;Kapteijn,F.;Moulijn,J.A.Ind.Eng.Chem.Res.2004,43,1211.Figure 2.External surface of the Co/SiO 2pellet and the capsule catalyst pellet and the EDS analysis result:(A)Co/SiO 2;(B)2-Co/SiO 2-zeolite;(C)Co/SiO 2;(D)2-Co/SiO 2-zeolite.1700Langmuir,Vol.21,No.5,2005Letterscatalyst supported on silica because of the quite different morphology.The thickness of the zeolite of the membrane was measured as about 10µm.The intensity of Si K R and Al K R X-ray signals from an EDX line scan is also shown in Figure 3.The intensity of Al K R X-rays increased dra-matically at the zeolite membrane layer,while at the cen-ter of the catalyst,the Al K R X-ray intensity was near to zero.The Si signal intensity changed according to its con-tent in the Co/SiO 2FTS catalyst and HZSM5.The SiO 2/Al 2O 3ratio of the membrane of the capsule catalyst was 48.The catalytic properties of the catalysts were studied with a high-pressure flow-type fixed bed reactor.Co/SiO 2catalyst only and its mechanical mixture with zeolite (20wt %)were operated in the same conditions as a comparison.All the capsule catalysts gave similar CO conversion,which was slightly lower than mixture catalyst or normal FTS catalyst Co/SiO 2,probably because the zeolite membrane slowed the diffusion rate of CO and H 2as shown in Table 1.Also,methane selectivities increased when the membrane was coated and increased when the zeolite coating amount increased.The low diffusion efficiency of CO and H 2led to a high H 2/CO ratio in the interior part of the catalyst pellet,which might increase methane selectivity,13because H 2diffuses more quickly than CO,especially inside small pores or channels.The CO 2in FTS reaction is mainly from WGS (water gas shift)reaction,and its selectivity hardly changed.The hydrocarbon distributions of conventional FT catalyst Co/SiO 2and the mixture catalyst (Co/SiO 2+zeolite)are compared in Figure 4A,B.The mixture catalyst gives a narrower distribution than the Co/SiO 2catalyst,because the waxy product migrating from the conventional FTS catalyst to the surface of zeolite catalysts was subject to secondary isomerization and hydrocracking,forming lighter hydrocarbons containing isoparaffins.The se-quential isomerization and hydrocracking reaction on zeolite reduced the selectivity of long-chain paraffins and remarkably enhanced the selectivity of light isoparaffins.Different from the random behavior in the mechanical mixture catalyst,all products,in the form of straight chains,from Co/SiO 2core FTS catalyst must enter zeolite channels and diffuse through the zeolite membrane in capsule catalysts,which ensures that all waxy products receive secondary reactions inside zeolite membrane.The hydrocarbon diffusion rate in zeolite membranedependsFigure 3.A cross-sectional image of one capsule catalyst (2-Co/SiO 2-zeolite)and the intensity of Si K R and Al K R X-ray signals from the EDX line scan indicated in theimage.Figure 4.FT synthesis product distribution on (A)Co/SiO 2,(B)Co/SiO 2+zeolite-MX,(C)2-Co/SiO 2-zeolite,and (D)1-Co/SiO 2-zeolite-S catalyst;H 2/CO )2;1.0MPa;W/F )10g ‚h/mol based on Co/SiO 2;533K.Table 1.FT Reaction Properties of Capsule Catalysts asampleCO conversion (%)CH 4selectivity (%)CO 2selectivity (%)isoparaffin/n -paraffinzeolite coating amount (%)Co/SiO 298.415.710.60Co/SiO 2-zeolite-MX b 93.616.98.00.4920.0mixed 1-Co/SiO 2-zeolite c 83.622.79.950.3711.52-Co/SiO 2-zeolite 85.531.310.20.7317.27-Co/SiO 2-zeolite 86.137.47.0 1.8824.31-Co/SiO 2-zeolite-S d 91.524.310.4 1.2129.12-Co/SiO 2-zeolite e80.129.96.50.5117.2aReaction conditions:533K,1.0MPa,W/F )10g ‚h ‚mol -1,H 2/CO )2.b MX in the name of sample means the physical mixture of Co/SiO 2catalyst and zeolite whose zeolite additive is 20%.c Numbers in sample names represent crystallization time in days in zeolite synthesis.d S in the sample name means the catalyst was prepared from small Co/SiO 2pellets (0.38-0.50mm),while the others were prepared from large pellets (0.85-1.7mm).e W/F )5g ‚h ‚mol -1and other reaction conditions were the same.Letters Langmuir,Vol.21,No.5,20051701on chain length.Consequently,long-chain compounds stayed in the zeolite membrane longer,which caused all the long-chain hydrocarbons to crack and isomerize.All capsule catalysts gave a very sharp hydrocarbon distribu-tion that ended at C9-C10,while there were still some C13-C20hydrocarbons in the products of the mechanical mixture catalyst.Figure4C,D shows the hydrocarbon distribution for two typical capsule catalysts.It is sug-gested that the covering membrane had an excellent selectivity for short-chain hydrocarbons,inhibiting the long-chain hydrocarbon completely.In addition,the capsule catalyst produced much isoparaffins and olefins. The yield of isoparaffin depended on the zeolite membrane content,which is also listed in Table1.With the increase of zeolite membrane content,the ratio of isoparaffin to n-paraffin(>C3)increased.With a similar zeolite content, the capsule catalyst(2-Co/SiO2-zeolite)produced rather more isoparaffins than the mixture catalyst.These findings indicate that zeolite membrane had higher secondary reaction efficiency than the mechanically mixed zeolite because the capsule catalyst avoided the random occurrence of the secondary reactions of FTS hydrocarbons in the mechanical mixture catalyst.Also compared with the2-Co/SiO2-zeolite catalyst in Table1,when contact time W/F changed from10to5 g‚h‚mol-1,CO conversion decreased slightly due to the faster flow rate.Methane selectivity decreased and the ratio of isoparaffin to normal paraffin became lower,indicating the residence time of normal paraffins from the core FTS catalyst,inside zeolite membrane,was too short to receive enough isomerization and hydrocracking, for this consecutive reaction regime.CO2selectivity was down because the amount of water formed was reduced, related to the decreased CO conversion.Moreover,the capsule catalyst prepared from small FTS silica support pellets which crystallized in24h(1-Co/ SiO2-zeolite-S)showed a higher isoparaffin/n-paraffin ratio than the catalyst prepared from large silica pellets in48 h crystallization(2-Co/SiO2-zeolite)but a lower methane selectivity.It was implied that the pellet size of the core catalyst had a strong effect on the capsule catalyst properties.Modifying the membrane catalyst and the core catalyst or optimizing the reaction conditions might enhance the catalytic activity and selectivity of capsule catalysts.Further studies are needed soon. Furthermore,the typical chemical process can be represented asBuilding catalyst Cat1as a membrane on the surface of catalyst Cat2pellets can be applied to prepare a lot of capsule catalysts.This process can realize the combination of these two sequential reactions coupled with the in situ reaction-separation effect.These new kinds of capsule catalysts can be applied to many fields of chemical processes.LA047217H(13)Madon,R.J.;Iglesia,E.J.Catal.1994,149,428.A98Cat1B98Cat2C1702Langmuir,Vol.21,No.5,2005Letters。
羰基化合物直接还原胺化合成伯胺催化剂研究进展
化工进展Chemical Industry and Engineering Progress2022年第41卷第6期羰基化合物直接还原胺化合成伯胺催化剂研究进展吴静航1，陈臣举1，2，梁杰1，2，张春雷1，2（1上海师范大学化学与材料科学学院，上海200234；2上海绿色能源化工工程技术研究中心，上海200234）摘要：胺类化合物是一类重要的化工原料和中间体，在农药、医药、染料、高分子聚合物等领域有着广泛的应用。
通过羰基化合物（醛或酮类）的还原胺化来制备胺类化合物是当前的研究热点。
研究表明，贵金属基和非贵金属基的多相和均相催化剂均能够高效催化醛或酮类的还原胺化反应。
本文对近年来羰基化合物直接还原胺化（或一锅法）合成伯胺的研究现状进行了综述，包括还原胺化反应、催化剂、反应条件、底物适用范围和催化作用机制等，其中重点阐述了直接还原胺化催化剂的研究进展。
文章指出：通常多相催化剂具有活性高以及可重复使用等优点，而均相催化剂的优势在于催化效率高，伯胺选择性高；另一方面，以Pd 、Rh 、Ru 等为代表的贵金属催化剂催化性能优异，但价格昂贵，因此可采用Co 、Ni 等性能同样优异但价格相对低廉的非贵金属催化剂以降低成本。
文中提出，催化效率高、反应条件温和、普适性高的羰基化合物还原胺化催化剂应成为未来重点研究方向。
关键词：直接还原胺化；羰基化合物；伯胺；均相催化；多相催化；催化剂中图分类号：O622.6；O622.4文献标志码：A文章编号：1000-6613（2022）06-2981-12Recent progress in the synthesis of primary amine via direct reductiveamination of aldehydes and ketonesWU Jinghang 1，CHEN Chenju 1，2，LIANG Jie 1，2，ZHANG Chunlei 1，2(1College of Chemistry and Materials Science,Shanghai Normal University,Shanghai 200234,China;2ShanghaiEngineering Research Center of Green Energy Chemical Engineering,Shanghai 200234,China)Abstract:Amines,especially primary amines,have been extensively employed in pesticide,medicine,dye and high molecular polymer as raw materials or intermediates.Recently,direct reductive amination of carbonyl compounds (aldehydes or ketones)has been a research focus for synthesizing primary amines.Heterogeneous and homogeneous catalysts based on noble and non-noble metals have been proven to be efficient for direct reductive amination of carbonyl compounds.In this paper,we carefully review the state of art of direct reductive amination of carbonyl compounds (one-pot method)to synthesize primary amines,including reaction profile,recent progress in catalysts,reaction conditions,the substrate scope and catalytic mechanism,especially the catalysts.Generally,heterogeneous catalysts are highly active and could be reused,while homogeneous catalysts have the advantages of high efficiency and high primary amines selectivity.On the other hand,noble catalysts like Pd,Rh and Ru are more active and expensive,so non-noble metal based catalysts like Co and Ni catalysts could be alternative for the sake of economic.Thus,the catalysts for direct reductive amination to synthesize primary amines with high efficiency,mild综述与专论DOI ：10.16085/j.issn.1000-6613.2021-1551收稿日期：2021-07-21；修改稿日期：2021-11-19。
树莓胶体模板法
树莓胶体模板法
近日，来自美国哈佛大学的Joanna Aizenberg教授团队的科研人员在Nature Catalysis发表了题为“Nanoparticle proximity controls selectivity in benzaldehyde hydrogenation”的论文，该项研究采用了一种模块化树莓胶体模板方法来调整PdAu合金纳米粒子的平均粒子间距，同时保留所有其他理化性质，包括纳米粒子尺寸。
通过控制三维大孔SiO2载体中的金属负载量和预成形纳米粒子的位置，并利用苯甲醛加氢生成苯甲醇和甲苯作为探针反应，研究人员发现增加粒子间距（从12 nm到21 nm）可大幅提高对苯甲醇的选择性（从54%提高到99%），且不影响催化性能。
直链淀粉手性固定相拆分西那卡塞对映体
直链淀粉手性固定相拆分西那卡塞对映体卢定强;孙生柏;凌岫泉;王琦;夏芙洁【期刊名称】《化学研究与应用》【年(卷),期】2015(000)006【摘要】A quantitative analysis method for the determination of cinacalcet enantiomers by HPLC had been developed. The enanti-omers of cinacalcet were separated on a Chiralpak AD-H column and the UV detection wavelength was 224 nm. The influences of concentration of organic solvent,proportion of triethylamine,column temperature and flow rate on the enantiomeric separation were investigated. The optimal chromatographic conditions were as follows:the mobile phase was hexane-isopropanol-triethylamine(90∶10∶0. 1,V/V/V);the flow rate was 1. 0 mL·min-1;the column temperature was 30℃. Under the optimal conditions,the elution order of two enantiomers was S-cinacalcet before R-cinacalcet. It was simple,accurate,and reproducible HPLC method,and could be used for the analysis and quality control of cinacalcet.%建立了一种快速、准确的高效液相色谱分析方法。
西酞普兰对映体的手性色谱拆分及吸附平衡
西酞普兰对映体的手性色谱拆分及吸附平衡徐倩倩;苏宝根;鲍宗必;邢华斌;杨亦文;任其龙【摘要】The enantioseparation of citalopram enantiomers was investigated using high performance liquid chromatography to optimize chromatographic conditions. Chiral stationary phases ( CSPs) including derivatized polysaccharide CSPs, crosslinked diallyltartrinine amide CSPs and cyclodextrin-based CPSs were used as stationary phases. N-Hexane with a small amount of diethylamine (0. 1% , volume) modified with methanol, ethanol and 2-propanol were used as mobile phase. The influence on retention factor, enantioselectivity, resolution, theoretical plates and asymmetry factor were studied. The effect of temperature was also investigated on the most favorable CSP and mobile phase. Chiralpak AD-H (derivatized polysaccharide CSP) and 2-propanol were proved to be the most favorable CSP and modifier, and 5% (vol) of 2-propanol was the preferred concentration. It was found that among the temperature range of 293. 15-308. 15 K, higher temperature was favorable to the enantioseparation. The adsorption isotherms of citalopram enantiomers were determined by frontal analysis chromatography under the optimized chromatographic conditions. The isotherms showed convex shape and well fitted by the Langmuir adsorption isotherm model. This work provides the basic data for separation of citalopram on SMB.%以添加醇类和二乙胺的正己烷为流动相,考察了多糖类、酒石酸类和环糊精类手性固定相对西酞普兰外消旋体的拆分效果,优选合适的手性固定相、流动相和温度等色谱条件,在此基础上利用前沿色谱法测定了西酞普兰对映体的吸附等温线.优化的色谱操作条件为:Chiralpak ADH柱为固定相,正己烷:异丙醇:二乙胺(95∶5∶0.1,体积比)为流动相,柱温35℃.西酞普兰对映体的吸附等温线为优惠型,采用Langmuir方程拟合,效果较好.本研究为模拟移动床(SMB)制备西酞普兰对映体提供重要的基础数据.【期刊名称】《化工学报》【年(卷),期】2012(063)004【总页数】7页(P1095-1101)【关键词】西酞普兰;手性色谱分离;吸附等温线【作者】徐倩倩;苏宝根;鲍宗必;邢华斌;杨亦文;任其龙【作者单位】浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027;浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027;浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027;浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027;浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027;浙江大学生物质化工教育部重点实验室,化学工程与生物工程学系,浙江杭州310027【正文语种】中文【中图分类】TQ016.1抗抑郁药物西酞普兰最早由丹麦Lundbeck公司研制，1989年首先在丹麦上市［1－2］，1998年美国FDA批准该药物在美国上市。
奥沙普嗪的化学结构修饰研究
奥沙普嗪的化学结构修饰研究研究方案：奥沙普嗪是一种广泛应用于心理疾病治疗的药物，它的主要作用机制是通过调节神经递质的平衡来改善神经系统功能。
然而，奥沙普嗪的反应性差异和不良反应限制了其临床应用。
本研究的目标是探索奥沙普嗪化学结构的修饰，以提高其药效和减少不良反应。
1. 研究方法：1.1. 结构修饰方法：采用合成化学方法对奥沙普嗪的结构进行修饰。
通过合理的设计和合成化合物的方法学选择，合成一系列的新奥沙普嗪衍生物。
然后，通过核心结构变化和侧链修饰等手段，制备不同结构的化合物。
1.2. 神经递质调节研究：利用细胞模型和动物实验评估修饰后化合物对神经递质的调节作用。
使用神经细胞系（如SH-SY5Y细胞）作为模型，通过Western blot、免疫荧光染色等方法检测修饰后化合物对神经递质受体表达和信号通路的影响。
使用动物模型（如小鼠）评估修饰后化合物对行为的调节作用，如运动活性、记忆和学习等。
1.3. 不良反应评估：通过建立体外和体内的不良反应预测模型，评估修饰后化合物的不良反应。
体外模型可以使用细胞毒性实验、细胞凋亡检测等方法，体内模型可以使用小鼠模型进行评估。
2. 实验设计：2.1. 合成新化合物：根据奥沙普嗪的结构和已有研究，设计合成方案，合成一系列的新奥沙普嗪衍生物。
对修饰后的化合物进行表征，如质谱、红外光谱、核磁共振等。
2.2. 细胞实验：选取经过修饰的化合物，评估其对神经递质受体的调节作用。
使用细胞系如SH-SY5Y细胞，通过Western blot和免疫荧光染色等方法分析修饰后化合物对关键通路蛋白的影响。
2.3. 动物实验：选择表现出较好神经递质调节效果的化合物，使用小鼠模型评估其对行为的调节作用。
通过行为学实验，如开放场实验、Y字迷宫实验等，评估修饰后化合物对小鼠的活动性、学习和记忆的影响。
2.4. 不良反应评估：通过体外细胞毒性实验和体内小鼠模型评估修饰后化合物的不良反应。
观察细胞的存活率和损伤情况，以及小鼠的运动能力、器官功能等，以评估其潜在的毒性和不良反应。
噻吩并咔唑稠环基有机光敏剂的合成及其光伏性能研究
噻吩并咔唑稠环基有机光敏剂的合成及其光伏性能研究有机光敏剂是有机太阳能电池(OSCs)的核心部分,它自身的物理和化学性质决定着电池的光伏性能。
因此,为进一步提升OSCs的能量转换效率,开发综合性能优良的新型有机光敏材料具有重要研究意义。
本文开发了系列噻吩并咔唑稠环(DTCC)基有机光敏剂,并采用核磁共振谱、质谱以及红外光谱等进行了结构表征。
此外,我们还采用理论计算、紫外-可见吸收光谱和循环伏安等系统地研究了该类材料的光物理和电化学性质。
基于合成的光敏材料,我们构建了OSCs,并探讨了材料结构与光伏性能之间的关系。
主要研究结果如下:1、以DTCC为电子给体(D)和3-(二氰基亚甲基)靛酮为电子受体(A),设计并合成了具有A-D-A构型的n-型有机半导体材料(DTCC-IC)。
结果表明:DTCC-IC在500-720 nm具有强的光捕获能力和高的摩尔消光系数(>105 M-1 cm-1),具有合适的HOMO/LUMO能级(-5.50/-3.87 eV)。
空间电荷限制电流法测试表明:DTCC-IC的电子迁移率高达2.17×10-3cm2 V-1s-1,这可与富勒烯衍生物受体相媲美。
在模拟太阳光(AM 1.5G,100 mWcm-2)照射下,基于聚合物给体PTB7-Th和DTCC-IC受体构建的本体异质结太阳能电池,获得的最高能源转换效率达6%。
这表明DTCC是一类综合性能优异的电子给体构建单元,可用于开发高迁移率n-型有机半导体材料。
2、基于DTCC单元,设计并合成了系列D-A-π-A型有机染料C1-C3。
其中,DTCC为电子给体,苯环为共轭桥连单元,羧酸为锚定基团。
为了调控染料的分子骨架结构、吸收光谱、能级结构以及光伏性能,我们将第二辅助受体(譬如,苯并噻二唑,BT;二氟苯并噻二唑,DFBT;和吡啶噻二唑,PT)引入到染料C1-C3的分子骨架中。
结果表明:强的D-A效应使得染料C1-C3具有强的分子内电荷转移和高的摩尔消光系数(>3.14×104 M-1 cm-1),这确保了该类染料具有强的光捕获能力;相比BT-基染料C1,DFBT-基染料C2中的氟取代破坏了分子骨架的共平面性,使得C2的电荷转移吸收峰发生了 7 nm的蓝移。
手性氮丙啶试剂的合成
手性氮丙啶试剂的合成
何永炳;肖元晶;孟令芝;吴成泰
【期刊名称】《厦门大学学报：自然科学版》
【年(卷),期】1999(0)S1
【总页数】1页(P209-209)
【关键词】氮丙啶;固体化合物;手性氨基酸;武汉大学;亲电试剂;胺类化合物;有机合成;科技创新基金;化学系;合成进展
【作者】何永炳;肖元晶;孟令芝;吴成泰
【作者单位】武汉大学化学系
【正文语种】中文
【中图分类】O626
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