Corona-induced electrohydrodynamic instabilities in low conducting liquids

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超声引导下微波消融联合贝伐珠单抗治疗晚期结肠癌伴肝转移的临床价值

超声引导下微波消融联合贝伐珠单抗治疗晚期结肠癌伴肝转移的临床价值

·临床研究·超声引导下微波消融联合贝伐珠单抗治疗晚期结肠癌伴肝转移的临床价值韩小军袁理郭道宁摘要目的探讨超声引导下微波消融联合贝伐珠单抗治疗晚期结肠癌伴肝转移的临床应用价值。

方法选取在我院就诊的102例晚期结肠癌伴肝转移患者,按随机数字表法分为观察组和对照组各51例,对照组采用贝伐珠单抗联合常规化疗治疗,观察组在此基础上采用超声引导下微波消融治疗;比较两组患者治疗后疗效、免疫功能、不良反应及预后情况。

结果治疗后,观察组客观缓解率(ORR)、疾病控制率(DCR)均高于对照组(均P<0.05);两组CD3+、CD4+、CD8+均较治疗前下降,且观察组CD3+、CD4+、CD4+/CD8+均高于对照组,CD8+低于对照组,差异均有统计学意义(均P<0.05)。

治疗后,两组胃肠道反应、食欲减退、疲劳乏力等不良反应比较差异均无统计学意义;观察组累积无复发生存率及累积总生存率分别为78.77%、57.45%,均高于对照组(49.32%、34.23%),差异均有统计学意义(χ2=10.086、4.536,P=0.001、0.033)。

结论超声引导下微波消融联合贝伐珠单抗能提高晚期结肠癌伴肝转移患者的治疗效果,缓解免疫功能抑制,改善生存状况,具有较好的临床应用价值。

关键词超声引导;微波消融;结肠癌,晚期;肝转移;贝伐珠单抗[中图法分类号]R445.1[文献标识码]AClinical value of ultrasound-guided microwave ablation combined withbevacizumab in the treatment of advanced colonadenocarcinoma with liver metastasisHAN Xiaojun,YUAN Li,GUO DaoningDepartment of Ultrasound Medicine,Mianyang Hospital Affiliated to School of Medicine,University of Electronic Science andTechnology of China,Sichuan621000,ChinaABSTRACT Objective To explore the application clinical value of ultrasound-guided microwave ablation combined with bevacizumab in the treatment of advanced colon adenocarcinoma(COAD)with liver metastasis.Methods A total of102 patients with advanced COAD with liver metastasis treated in our hospital were selected,and divided into the observation group and the control group by random number table method,with51cases in each group.The control group was treated with bevacizumab combined with conventional chemotherapy.On this basis,the observation group was treated with ultrasound-guided microwave thermal ablation.The curative effect,immune function,adverse reactions and prognosis after treatment of the two groups were compared.Results After treatment,the objective remission rate(ORR)and disease control rate(DCR)in the observation group were higher than those in the control group(both P<0.05).After treatment,the CD3+,CD4+and CD4/CD8+in the observation group were higher than those in the control group,and CD8+was lower than that in the control group,the differences were statistically significant(all P<0.05).After treatment,there were no statistically significant difference in the incidence rates of adverse reactions such as gastrointestinal reactions,loss of appetite and fatigue between the two groups.The cumulative recurrence-free survival rate and cumulative overall survival rate in observation group were78.77%and57.45% respectively,which were significantly higher than those in control group(49.32%and34.23%),the differences were statistically significant(χ2=10.086,4.536,P=0.001,0.033).Conclusion Ultrasound-guided microwave ablation combined with作者单位:621000四川省绵阳市,电子科技大学医学院附属绵阳医院绵阳市中心医院超声医学科(韩小军、郭道宁),肿瘤科(袁理)通讯作者:郭道宁,Email:******************结肠癌是常见的消化道肿瘤,近年来其发病率和死亡率均逐渐升高。

吲哚结构的荧光探针在粘度检测及细胞成像中的应用

吲哚结构的荧光探针在粘度检测及细胞成像中的应用

第42 卷第 9 期2023 年9 月Vol.42 No.91151~1156分析测试学报FENXI CESHI XUEBAO(Journal of Instrumental Analysis)吲哚结构的荧光探针在粘度检测及细胞成像中的应用余 强1,李祥1,马素芳2*(1.山西医科大学医学影像学院,山西太原030001;2.山西医科大学基础医学院,山西太原030001)摘要:该文以1,2,3,3-四甲基-3H-吲哚鎓碘化物为电子受体,吲哚为电子供体,通过一步反应合成了一种D-π-A结构的新型荧光探针(1),并用于药物诱导的细胞中粘度变化的检测。

采用核磁氢谱(1H NMR)、核磁碳谱(13C NMR)、高分辨质谱(ESI-MS)和红外光谱(IR)对探针进行表征,通过荧光光谱考察了探针光学性质及响应粘度(η)的可行性。

在不同比例(g∶g)水-甘油体系中,探针的荧光强度(I)随着甘油比例的增大逐渐增强,当甘油比例为90%时,探针荧光强度约增强100倍。

Förster-Hoffmann方程分析结果显示,lg I与lgη具有较好的线性关系(r2 = 0.998 0),探针对粘度的检出限为1.167 cP。

同时该探针对粘度具有较好的选择特异性、光稳定性和pH值稳定性。

将探针与经鱼藤酮或羰基氰化氯苯腙(CCCP)刺激的HeLa细胞共孵育30 min,细胞荧光亮度明显增强,表明探针具有较好的生物相容性,可以对细胞微环境中粘度的变化进行有效响应。

所制备的探针具有稳定性好、特异性强、生物相容性好的优点,具有一定的生物应用潜质。

关键词:粘度响应;吲哚;荧光探针;细胞成像中图分类号:O657.3;Q334文献标识码:A 文章编号:1004-4957(2023)09-1151-06Application of Fluorescence Probe Based on Indole in ViscosityDetection and Cell ImagingYU Qiang1,LI Xiang1,MA Su-fang2*(1.Medical Imaging Department,Shanxi Medical University,Taiyuan 030001,China;2.School of BasicMedical Science,Shanxi Medical University,Taiyuan 030001,China)Abstract:In this paper,a novel fluorescent probe with D-π-A structure(1) was synthesized by a one-step reaction using 1,2,3,3-tetramethyl-3H-indolium iodide as an electron acceptor and in⁃dole as an electron donor for the detection of drug-induced viscosity changes in cells. The structure of the fluorescent probe was characterized by nuclear magnetic hydrogen spectroscopy(1H NMR),nu⁃clear magnetic carbon spectroscopy(13C NMR)and electrospray ionization mass spectrometry(ESI-MS). The optical properties of the probe and the feasibility of response viscosity(η) were measured by fluorescence spectroscopy. The probe was added to different ratios of water-glycerol system,the fluorescence intensity(I) of probe increased gradually with the increasing ratio of glycerol. When the ratio of glycerol was 90%,the fluorescence intensity of the probe was enhanced by about 100 times compared with the pure water system.The analysis using the Förster-Hoffmann equation showed a good linear relationship between lg I and lgη(r2= 0.998 0),and the lowest detection limit of the probe for viscosity was 1.167 cP,indicating the probe has good sensitivity to viscosity response and has the potential for quantitative viscosity detection. The probe did not respond to other active mole⁃cules,and the fluorescence intensity was little affected by organic solvents with small viscosity,and only had a better response to glycerol with large viscosity,which fully indicates that the probe degree has an excellent specificity to viscosity. The fluorescence of the probe both in the aqueous solution and the water-glycerol(90%) solution did not change significantly after 60 min keeping at room tem⁃perature.The fluorescence intensities of the probe both in aqueous solution and the water-glycerol (90%) solution were almost unchanged in the pH range of 4.0-9.0,which indicated that the probe has good photostability and pH stability. The probe had a low effect on cell viability within the experi⁃收稿日期:2023-03-21;修回日期:2023-06-02基金项目:国家自然科学基金资助项目(82202289,82071969)∗通讯作者:马素芳,博士,讲师,研究方向:小分子荧光探针的构建及应用,E-mail:masufang@doi:10.19969/j.fxcsxb.230321021152分析测试学报第 42 卷mental range,indicating that the probe has good biocompatibility. In addition,only weak fluores⁃cence was observed after HeLa cells were co-incubated with the probe solution for 30 min. In con⁃trast,after the probe solution was co-incubated with HeLa cells which were stimulated with rotenone and carbonyl cyanide chlorophenylhydrazone(CCCP) for 30 min,a significant increase in cell fluo⁃rescence brightness could be observed,indicating that the probe can effectively detect changes in vis⁃cosity in the cell microenvironment. All the above results indicate that the probe has the advantages of good stability,specificity and biocompatibility as a viscosity-responsive probe,and has excellent potential for biological applications.Key words:viscosity response;indole;fluorescent probe;cell imaging粘度作为细胞微环境的重要参数之一,不仅对细胞内信号转导和新陈代谢具有重要意义,而且能够通过影响活细胞内生物分子和化学信号的相互作用直接或间接影响细胞的各种生理功能,如自噬等[1-5]。

LCMS专用名词解释

LCMS专用名词解释

Liquid Chromatography–Mass Spectrometry:An Introduction.Robert E.ArdreyCopyright¶2003John Wiley&Sons,Ltd.ISBNs:0-471-49799-1(HB);0-471-49801-7(PB) Glossary of TermsThis section contains a glossary of terms,all of which are used in the text.Itis not intended to be exhaustive,but to explain briefly those terms which often cause difficulties or may be confusing to the inexperienced reader.Accuracy The closeness of a result to its true value.Accurate mass The m/z ratio of an ion determined to high accuracy to enablethe elemental composition of the ion to be determined.Adduct ion An ion arising from the combination of two species,e.g.the molec-ular species observed in a positive-ion APCI spectrum is usually an adduct ofthe analyte molecule with a species such as H+,Na+or NH4+.Aerospray An atmospheric-pressure ionization technique in which dropletsare formed from a liquid stream by a combination of heat and a nebuliz-ing gas and ions are formed by ion evaporation rather than ion–molecule reactions.Affinity chromatography A form of chromatography in which separation is achieved by utilizing highly specific biochemical interactions,such as steric-or charge-related conditions,between the analyte and a molecule immobilizedon a column.It is different from most forms of chromatography in that analytesdo not continuously elute from the column–only those that interact with the stationary phase are retained and thus separated from other components ofthe mixture under investigation.These immobilized materials are eluted fromthe column after all other materials have been removed.Atmospheric-pressure chemical ionization(APCI)An ionization method in which a liquid stream is passed through a heated capillary and a concentricflow of a nebulizing gas.Ions are formed by ion–molecule reactions betweenthe analyte and species derived from the HPLC mobile phase.Atmospheric-pressure ionization(API)A general term used for all forms of ionization that take place at atmospheric pressure.248Liquid Chromatography–Mass Spectrometry Background-subtracted spectrum A mass spectrum from which ions aris-ing from species other than the analyte have been removed by computer manipulation.Base peak The most intense ion in a mass spectrum.The intensity of other ions in the spectrum are reported as a percentage of the intensity of the base peak. Biotransformation An alternative term for drug metabolism.Buffer An electrolyte added to the HPLC mobile phase.Capacity factor The parameter used in HPLC to measure the retention of an analyte.Capillary column This term refers to a chromatographic column of‘small’diameter and is used in both gas and high performance liquid chromatogra-phy.In HPLC,the term is usually applied to columns with internal diameters of between0.1and2mm.The term microbore column is often used synony-mously to describe these columns but is more correctly applied to columns with internal diameters of1or2mm.Charge-residue mechanism One of the two mechanisms used to account for the production of ions by electrospray ionization.Chemical ionization An ionization method used to maximize the production of intact molecular ed for volatile,thermally stable analytes. Chemical noise Signals from species other than the analyte present in the sys-tem or sample that cannot be resolved from that of the analyte. Chromatographic selectivity The degree to which compounds are separated on a particular chromatographic system.Chromatography General term for a number of methods used to separate the individual components of a mixture.Collision energy The energy of the collision between an ion and a gas molecule which may be used to vary the amount of fragmentation observed. Collision-induced dissociation Fragmentation of an ion by collision with a gas molecule.Concentration-sensitive detector A detector for which the intensity of re-sponse is proportional to the concentration of analyte reaching it.Cone-voltage fragmentation Fragmentation of ions,commonly produced by APCI or electrospray ionization,effected by the application of a voltage within the source of the mass spectrometer.Constant-neutral-loss scan An MS–MS scan in which ions containing a par-ticular structural feature may be identified.Corona discharge Occurs when thefield at the tip of the electrode is suffi-ciently high to ionize the gas surrounding it but insufficiently high to cause a spark.An integral part of the APCI interface.Coulombic explosion The process by which a droplet disintegrates into a number of smaller droplets which occurs when the repulsive forces between charges on the surface of a droplet are greater than the cohesive force of surface tension.Glossary of Terms249 Diode-array UV detector A UV detector which monitors all wavelengths simultaneously and therefore allows a complete UV spectrum to be obtained instantaneously.The alternative,a dispersive UV detector,monitors one wave-length at a time and thus requires a considerable amount of time to record a complete spectrum.Discharge electrode An electrode used to generate a corona discharge. Double-focusing mass spectrometer A mass spectrometer consisting of elec-trostatic and magnetic sector analysers capable of achieving high-mass spectral resolution.Drug metabolism The process by which drugs are transformed in the body to a form that is more readily eliminated.Dynamic range(of a detector)The range over which the addition of further analyte brings about an increase,however small,in detector response. Edman degradation A method of amino acid sequencing in proteins in which successive N-terminal amino acids are removed from the polypeptide chain and identified.Electrohydrodynamic ionization A process in which a high voltage is used to generate droplets from which ions are desorbed under conditions of high vacuum.Electron ionization An ionization method employed in mass spectrometry in which analytes,in the vapour phase,are bombarded with high-energy electrons. Electrospray The process whereby a liquid stream is broken up into droplets by the action of a high potential.Electrospray ionization The production of ions from droplets produced by the electrospray process.Electrostatic analyser(ESA)An energy-focusing device used in a double-focusing mass spectrometer to increase mass spectral resolution.Energy-sudden ionization technique One in which energy is provided to a thermally labile molecule so rapidly that it is desorbed and ionized before decomposition takes place.Enzyme digestion The treating of a protein with a proteolytic enzyme to form a number of smaller peptides which may then be sequenced. Experimental design A number of formal procedures whereby the effect of experimental variables on the outcome of an experiment may be assessed. These may be used to assess the optimum conditions for an experiment and to maximize the accuracy and precision obtained.External standard A method of relating the intensity of a signal from an analyte measured in an‘unknown’to the amount of analyte present.This method consists of running a series of standards containing known amounts of the analyte independently from the samples to be determined.Factor An experimental variable that has(or may have)an effect on the out-come of an experiment,e.g.temperature,concentration of reactants,presence of a catalyst,etc.250Liquid Chromatography–Mass Spectrometry Factorial design One method of experimental design that allows interactions between factors to be investigated,i.e.whether changing one experimental variable changes the optimum value of another.Fast-atom bombardment An ionization method used for involatile and ther-mally labile materials.In this technique,the sample is dissolved in a matrix material and bombarded with a high-energy atom or ion beam.Field desorption An ionization method in which sample is deposited on a wire to which a high voltage is applied.Flow programming Varying the HPLCflow rate during the course of a separation.Forward-geometry double-focusing mass spectrometer A double-focusing mass spectrometer in which the electrostatic analyser precedes the magnetic analyser.Four-sector mass spectrometer A mass spectrometer used for MS–MS studies consisting of two double-focusing mass spectrometers in series. Fragmentor voltage Another term for cone-voltage fragmentation.General detector A(chromatographic)detector which responds to all com-pounds reaching it.Glycoprotein A protein containing sugar molecules attached to its polypep-tide chain.Glycosylation The incorporation of a sugar molecule into a protein. Gradient elution The changing of HPLC mobile phase composition during the course of an analysis.High-resolution mass spectrometer A mass spectrometer capable of high res-olution and measuring m/z ratios with high accuracy to enable the atomic composition of an ion to be determined.Hybrid mass spectrometer An MS–MS instrument combining magnetic sector and quadrupole mass analysers.Hybrid technique The combination of two or more analytical techniques. Hyphenated technique The combination of two analytical techniques. Injector A common term for the method of sample introduction into a chro-matographic system.In-source fragmentation(see Cone-voltage fragmentation)Interface The hardware employed to link two analytical techniques.The pri-mary purpose of an interface is to ensure that the operational requirements of each of the techniques are not compromised by the other.Interference A species other than the analyte of interest which gives a detec-tor response.Internal standard A method of relating the intensity of signal from an analyte measured in an‘unknown’to the amount of analyte present.In this approach, a known amount of an internal standard is added to both calibration andGlossary of Terms251‘unknown’samples and the ratio of signal intensities of the analyte and internal standard in each is calculated.This method of standardization improves both accuracy and precision.Ion evaporation One of the two mechanisms used to account for the production of ions by electrospray ionization.Ion–molecule reaction The reaction between an ion and a neutral molecule which leads to the production of an adduct ion.Ion-pairing reagent A compound that forms a complex with an ionic com-pound to allow its analysis using HPLC.Ionspray Pneumatically assisted electrospray–a process in which nebuliz-ing gas is used in conjunction with a high voltage to form droplets from a liquid stream.Ion-trap A low-resolution mass analyser.Isocratic elution The use of a mobile phase of constant composition during the course of an analysis.LC–MS–MS The combination of HPLC with MS–MS.Library searching The use of a computer to compare a mass spectrum to be identified with large numbers of reference spectra.Limit of detection The smallest quantity of an analyte that can be detected reliably.Limit of quantitation The smallest quantity of an analyte that can be deter-mined with accuracy and precision.Linear range The range of concentrations over which the analytical signal is directly proportional to the amount of analyte present.Linked scanning A series of techniques in which the electrostatic analyser voltage and magneticfield strength of a double-focusing mass spectrometer are scanned to obtain MS–MS spectra.Low-resolution mass spectrometer A spectrometer which is capable of mea-suring the m/z ratio of an ion to the nearest integer value.Magnetic sector A low-resolution mass analyser in which the variation of a magneticfield is used to bring ions of different m/z ratios to a detector. Mass-analysed ion kinetic energy spectrometry(MIKES)A form of MS–MS product-ion scan that may be carried out on a reversed-geometry double-focusing mass spectrometer.Mass chromatogram(see Reconstructed ion chromatogram)Mass-flow-sensitive detector A detector for which the intensity of response is proportional to the amount of analyte reaching it.Mass-sensitive detector(see Mass-flow-sensitive detector)Matrix-assisted laser desorption ionization(MALDI)A method used for the ionization of high-molecular-weight compounds.In this approach,the ana-lyte is crystallized with a solid matrix and then bombarded with a laser of a frequency which is absorbed by the matrix material.252Liquid Chromatography–Mass Spectrometry Matrix effects An increase or decrease in signal intensity from an analyte due to the presence of any other materials in the sample in which it is being determined.Matrix material A material used in fast-atom bombardment and matrix-assisted laser desorption ionization to transfer energy to an analyte molecule to bring about its ionization.Maximum entropy A computer algorithm used to predict the theoretical signal from which that observed in a spectrum has been ed in conjunction with electrospray ionization to enhance the quality of the spectra obtained. McLafferty rearrangement A molecular rearrangement that occurs under cer-tain ionization conditions which results in the production of characteristic ions in the mass spectrum of the analyte from which it has been generated. Megaflow electrospray An electrospray system capable of producing droplets directly from HPLCflow rates of the order of1ml min−1(true electrospray is most efficient atflow rates of the order of10µl min−1).Microbore column(see Capillary column)Mobile phase That part of a chromatographic system which causes the analyte to move from the point of injection to the detector–in HPLC,this is a liquid. Molecular ion The ion in the mass spectrum corresponding to the unfragmented molecule under investigation.Monoisotopic molecular weight The molecular weight of an analyte,calcu-lated by using the masses of the more/most abundant isotopes of each of the elements present.MS–MS A number of techniques in which two stages of mass spectrometry are used in series to probe the relationship between ions formed from an analyte–also known as tandem mass spectrometry.MS n An extension of MS–MS in which more than two stages of mass spec-trometry are used to probe the relationship between ions formed from an analyte.Multiple-ion detection(see Selected-ion monitoring)Multiply charged ion An ion with more than one charge.The electrospray spectra from compounds of high molecular weight contain exclusively multiply charged ions.Murphy’s Law‘If something can go wrong it will do so and at the most inconvenient time!’†Nanoflow electrospray A form of electrospray ionization,carried out atflow rates of the order of nl min−1.Negative ionization The production of negative ions of analytical significance from the analyte of interest.Noise The change in detector response over a period of time in the absence of analyte.This consists of two components,namely the short-term random †As the majority of readers will confirm,this observation regularly holds true in all walks of life.Also known under various other names!Glossary of Terms253 variation in signal intensity,and the drift,i.e.the increase or decrease in the average noise level over a period of time.Normal-phase HPLC An HPLC system in which the mobile phase is less polar that the stationary phase.Packed column An HPLC column containing particles of inert material of typically5µm diameter on which the stationary phase is coated.Peptide A linear chain of a small number of amino acids linked by peptide bonds.The number of amino acids which differentiates between a protein and a peptide remains a matter for discussion.Peptide mapping The process of considering the amino acid sequence infor-mation from peptides obtained by enzyme digestion in an attempt to derive the(amino acid)sequence of the parent protein.Phase I metabolism The introduction of a polar group,e.g.an hydroxyl group, into a parent drug structure prior to its elimination from the body.Phase II metabolism The reaction of a phase I metabolite with an endogenous compound,e.g.glucuronic acid,to form a polar compound that is eliminated from the body.Plate height The width of a theoretical plate.Plate number The number of theoretical plates in a chromatographic column. This is a measure of the efficiency of the column.Polyimide belt The continuous belt used in the moving-belt LC–MS interface. Post-source decay The term used to describe the production of product-ion MS–MS spectra in a time-of-flight mass analyser.Post-translation modification Changes that occur to proteins after peptide-bond formation has occurred,e.g.glycosylation and acylation.Precision The closeness of replicate measurements on the same sample. Precursor-ion scan An MS–MS scan in which those ions that fragment to a given product ion are detected.Product-ion scan An MS–MS scan in which those ions obtained by fragmen-tation of a given precursor ion are detected.Protein A linear chain of amino acids linked by peptide bonds.Q–ToF The combination of quadrupole and time-of-flight mass analysers. This allows the m/z ratios of ions produced during a product-ion scan to be measured accurately and the elemental composition of these ions to be determined.Quadrupole A low-resolution mass analyser.Qualitative analysis The analysis of a sample to determine the identity of any compounds present.Quantitative analysis The analysis of a sample to determine the amount of an analyte present.Reagent gas A gas used in chemical ionization to produce species which react with molecules of the analyte of interest to produce a molecular species.254Liquid Chromatography–Mass Spectrometry Rearrangement ion An ion formed under certain ionization conditions in which the original molecular structure of the analyte has undergone some modifica-tion,i.e.has not been produced by simple bond scission.Reconstructed ion chromatogram A plot of the intensity of an ion of chosen m/z ratio as a function of analysis time.This is produced by computer analysis of mass spectral data acquired over an extended mass range.Reflectron An ion lens used in the time-of-flight mass analyser to increase the distance travelled by an ion and thereby increase the resolution of the instrument.Repeatability The closeness of a set of measurements carried out by a sin-gle analyst on a single instrument within a narrow time-interval using the same reagents.Repeller An electrode used in thermospray ionization to effect fragmentation of molecular species.Reproducibility The closeness of a set of measurements carried out by a num-ber of analysts on a number of instruments over an extended period. Resolution A term which indicates the ability of a device/technique to sepa-rate/distinguish between closely related signals.In chromatography,it relates to the ability to separate compounds with similar retention characteristics,and in mass spectrometry to the ability to separate ions of similar m/z ratios. Retention index The parameter used in gas chromatography to measure the retention of an analyte.Reverse-geometry double-focusing mass spectrometer A double-focusing mass spectrometer in which the magnetic analyser precedes the electrostatic analyser.Reversed-phase HPLC An HPLC system in which the mobile phase is more polar than the stationary phase.Selected-decomposition monitoring An MS–MS scan in which thefirst stage of mass spectrometry is set to transmit a selected ion and the second to trans-mit only a selected product ion.This technique increases the selectivity of the analysis.Selected-ion monitoring A technique in which the mass spectrometer is used to monitor only a small number of ions characteristic of the analyte of interest. Selected-ion recording(see Selected-ion monitoring)Selected-reaction monitoring(See Selected-decomposition monitoring) Selective detector A detector which responds only to compounds containing a certain structural feature.Selectivity The ability to determine the analyte of interest with accuracy and precision in the presence of other materials.Separation factor(see Chromatographic selectivity)Sequence tagging The use of MS–MS to investigate the amino acid sequence of a peptide.Glossary of Terms255 Sequencing The determination of the order in which the repeating units occur in a biopolymer,e.g.amino acids in a protein,sugar residues in a carbohy-drate,etc.Signal enhancement The increase in analyte signal intensity brought about by the presence of extraneous materials in the sample.Signal-to-noise ratio The ratio of the intensity of the analytical signal to that of the noise.This is used in determining the limits of detection and quantitation. Sodium dodecyl sulfate–polyacrylamide gel electrophoresis(SDS–PAGE) An electrophoretic technique used for the separation of proteins.Soft ionization technique An ionization technique that produces molecular species with few,if any,fragment ions.Solute-property detector A detector which monitors a property of the analyte, e.g.the UV detector.Solvent-property detector A detector which monitors a property of the HPLC mobile phase which is perturbed when an analyte elutes from the chromato-graphic column.Spray deposition A method used to apply HPLC eluate in later versions of the moving-belt interface to provide a uniform layer of mobile phase on the belt and thus minimize the production of droplets.Standard additions A method of relating the intensity of signal from an analyte measured in an‘unknown’to the amount of analyte present.This technique is designed to take matrix effects into account.Stationary phase That part of the chromatographic system with which the analytes interact,over which the mobile phaseflows.Suppression effects The decrease in analyte signal intensity brought about by the presence of extraneous materials in the sample.Tandem mass spectrometry An alternative term for MS–MS.Tandem technique An alternative term for the combination of two or more analytical techniques.Theoretical plate In plate theory,the chromatographic column is viewed as a series of narrow layers,known as theoretical plates,within each of which equilibration of the analyte between mobile and stationary phases occurs. Thermally labile compound A compound that decomposes under the influence of heat.Thermospray The process whereby a liquid stream is broken up into droplets by the action of a high temperature.Thermospray ionization The formation of ions from droplets produced by the thermospray process.Three-dimensional quadrupole(see Ion-trap)Time-of-flight mass analyser A mass analyser in which ions are separated‘in time’as they drift through afield-freeflight tube.Total-ion-current trace A plot of the total number of ions reaching the mass spectrometry detector as a function of analysis time.256Liquid Chromatography–Mass Spectrometry Transformation The mathematical process of changing a‘raw’electrospray spectrum containing a number of multiply charged ions into a mass spectrum plotted on a true mass scale.Triple quadrupole A mass spectrometer consisting of three sets of quadrupole rods in series,which is used extensively for studies involving MS–MS.Tri-sector mass spectrometer A mass spectrometer consisting of an electro-static analyser(ESA),a magnetic sector and a second ESA in series. Universal detector An alternative term for a general detector.Western blotting A means of transferring protein bands from an electrophoresis gel onto afixing medium for further analysis.Z-spray An electrospray source in which ions are extracted into the mass spec-trometer at90◦to the direction in which the spray is produced.MS Glossary on the Web/analyticalreview/mass spec/msglossary.htm。

内镜下NTAN注射术配合艾普拉唑治疗非静脉曲张性上消化道出血的效果分析

内镜下NTAN注射术配合艾普拉唑治疗非静脉曲张性上消化道出血的效果分析

DOI:10.19368/ki.2096-1782.2023.12.115内镜下NTAN注射术配合艾普拉唑治疗非静脉曲张性上消化道出血的效果分析董锦,杨红梅,姜中华盐城市第一人民医院消化内科,江苏盐城224000[摘要]目的分析内镜下NTAN注射术配合艾普拉唑治疗非静脉曲张性上消化道出血的临床疗效。

方法选取2021年11月—2022年11月盐城市第一人民医院收治的100例非静脉曲张性上消化道出血患者作为研究对象,按照随机数表法分为研究组与对照组,每组50例。

对照组采用艾普拉唑治疗,研究组在对照组基础上联用内镜下NTAN注射术,对比两组临床疗效。

结果研究组有效止血率为94.00%,高于对照组的80.00%,差异有统计学意义(χ2=4.332,P<0.05)。

研究组再出血率为4.00%,低于对照组的18.00%,差异有统计学意义(χ2=5.005,P<0.05)。

研究组不良反应发生率为4.00%,低于对照组的16.00%,差异有统计学意义(χ2=4.000,P<0.05)。

研究组治疗后促胃液素水平(73.28±4.06)μmol/L低于对照组(86.06±6.08)μmol/L,胆囊收缩素水平(12.47±1.00)μmol/L低于对照组(17.18±2.51)μmol/L,大便潜血转阴时间(2.20±0.84)d短于对照组(4.90±0.97)d,呕血停止时间(2.01±0.28)d短于对照组(4.03±0.49)d,住院时间(5.97±1.01)d短于对照组(9.79±2.13)d,差异有统计学意义(t=12.361、12.327、14.879、25.309、11.459,P<0.05)。

结论内镜下NTAN注射术配合艾普拉唑能够提高非静脉曲张性上消化道出血患者有效止血率,并加快免疫系统恢复,调节胃肠激素分泌平衡,且治疗安全性较高,具有良好的实用价值。

新型肿瘤学疗法!氧化铪纳米颗粒Nbtxr3治疗头颈癌(HNSCC):肿瘤部位激活,总生存期。。。

新型肿瘤学疗法!氧化铪纳米颗粒Nbtxr3治疗头颈癌(HNSCC):肿瘤部位激活,总生存期。。。

新型肿瘤学疗法!氧化铪纳⽶颗粒Nbtxr3治疗头颈癌(HNSCC):肿瘤部位激活,总⽣存期。

来源:本站原创 2021-10-28 02:20Nbtxr3具有⼀种物理作⽤机制(MoA),通过放疗激活,在所注射的肿瘤中诱导显著的肿瘤细胞死亡,随后触发适应性免疫反应和长期抗癌记忆。

头颈癌(图⽚来源:)2021年10⽉27⽇讯/⽣物⾕BIOON/ --Nanobiotix是⼀家处于后期临床阶段的⽣物技术公司,致⼒于开创颠覆性的、基于物理的治疗⽅法,为数百万患者带来⾰命性的治疗结果。

近⽇,该公司在2021年美国放射肿瘤学会(ASTRO)年会上公布了先导候选产品Nbtxr3治疗局部晚期头颈部鳞状细胞癌(LA-HNSCC)项⽬的新数据。

Nbtxr3是⼀种新型、潜在的⾸创(first-in-class)肿瘤学产品,由功能化氧化铪纳⽶颗粒组成,通过⼀次性瘤内注射给药,并通过放射激活。

该候选产品的物理作⽤机制(MoA)旨在通过放射激活时,在注射的肿瘤中诱导显著的肿瘤细胞死亡,随后触发适应性免疫反应和长期抗癌记忆。

考虑到物理MoA,Nanobiotix相信Nbtxr3可以扩展到任何可通过放疗治疗的实体肿瘤和任何治疗组合,特别是与免疫检查点抑制剂。

2020年2⽉,美国FDA已授予Nbtxr3快速通道资格(FTD):联⽤或不联⽤西妥昔单抗(cetuximab),⽤于治疗不适合铂类化疗的LA-HNSCC患者。

此次公布的数据来⾃⼀项多中⼼、开放标签、⾮随机、剂量递增和剂量扩展1期研究(Study102 Expansion),该研究正在评估Nbtxr3作为由放疗激活的单⼀药物,治疗不符合顺铂化疗资格且对西妥昔单抗不耐受的难治性⽼年和体弱LA-HNSCC患者的疗效和安全性。

数据显⽰,在可评估⼈群(n=41)中,中位总⽣存期(mOS)为18.1个⽉,中位⽆进展⽣存期(mPFS)为10.6个⽉。

⽽在整个⼈群(所有接受治疗的可评估和不可评估患者;n=54)中,mOS为14.1个⽉,mPFS为9.4个⽉。

微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷

微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷

第 29 卷第 4 期分析测试技术与仪器Volume 29 Number 4 2023年12月ANALYSIS AND TESTING TECHNOLOGY AND INSTRUMENTS Dec. 2023分析测试经验介绍(407 ~ 413)微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷陈丽梅,张 慧,白国涛,马彩霞,姚思雨,王 婧(呼和浩特海关技术中心,内蒙古呼和浩特 010020)摘要:采用微波灰化-电感耦合等离子体发射光谱法(ICP-OES)测定婴幼儿乳粉中钙、磷元素含量. 采用微波灰化法对婴幼儿乳粉进行前处理,正交试验方法确定微波灰化最佳条件,灰化后产物用2 mL硝酸溶液(体积比为1∶1)溶解后,用ICP-OES对钙、磷元素进行含量检测. 磷加标回收率为86%~104%,钙加标回收率为87%~96%.磷的相对标准偏差为2.5%~7.0%,钙的相对标准偏差为3.9%~10.0%,能够满足日常检测要求. 采用微波灰化法对婴幼儿乳粉中钙、磷元素进行样品前处理,相比微波消解方法,具有用时短、用酸量少、消解效果好、不需要进行赶酸处理等优点. 与干法灰化和湿法消解相比大大减少了样品处理时间. 采用微波灰化与ICP-OES结合对婴幼儿乳粉中的重要指标元素进行检测,在婴幼儿乳粉质量控制中有很好的应用价值.关键词:微波灰化;电感耦合等离子体发射光谱法;婴幼儿乳粉;钙;磷中图分类号:O657. 31 文献标志码:B 文章编号:1006-3757(2023)04-0407-07DOI:10.16495/j.1006-3757.2023.04.010Detemination of Calcium and Phosphorus in Infant Formula by Microwave Ashing- Inductive Coupled Plasma Emission SpectrometryCHEN Limei, ZHANG Hui, BAI Guotao, MA Caixia, YAO Siyu, WANG Jing(Technology Center of Hohhot Custom, Hohhot 010020, China)Abstract:The microwave ashing-inductive coupled plasma emission spectrometry (ICP-OES ) was used to determine the content of calcium and phosphorus in infant formula. The method of microwave ashing was used to pretreatment of the infant formula. The optimization conditions were determined by orthogonal test. After the microwave ashing, the ashes were dissolved with 2 mL nitric acid solution (volume ratio was 1∶1). The ICP-OES was used to determine the content of calcium and phosphorus. The recoveries of phosphorus and calcium were 86%~104% and 87%~96%, respectively. The relative standard deviation of phosphorus and calcium were 2.5%~7.0% and 3.9%~10.0%, respectively, which could meet the detection requirements. Compared with the method of microwave digestion, microwave ashing has the advantages of shorter time, less acid, better digestion effect and no need to drive acid treatment for calcium and phosphorus in infant formula. Compared with wet digestion and dry ashing, the sample processing time was greatly reduced. The detection of important index elements in infant formula by microwave ashing combined with ICP-OES has a good application value in the quality control of infant formula.Key words:microwave ashing;ICP-OES;infant formula;calcium;phosphorus收稿日期:2023−10−09; 修订日期:2023−12−12.基金项目:海关总署科研项目(批准号:2021HK186)[The Research Project of General Administration of Customs (2021HK186)]作者简介:陈丽梅(1981−),女,高级工程师,主要从事食品中元素检测工作,E-mail:******************.微波灰化技术是一种创新的样品前处理方法,利用抗热的密闭腔体及微波技术来加热,使得灰化速度提高,减少了能量损耗,增加了样品的处理量,工作环境清洁,使用安全. 不同于湿法酸消解,微波灰化的优点是处理过程比较简单,实验室日常工作非常通用,多用于过程及质量控制. 在石油工业、制药业、食品工业、塑料制品制造业、污染物治理等领域都有着广泛的应用. 微波灰化的原理是微波系统发射均匀的微波,穿透高温泡沫陶瓷护体,内置的耐高温泡沫瓷体内的碳化硅板将微波能量转化为热能,热量直接辐射到样品内,样品被均匀加热.微波的使用大大增加了加热效率,相较于传统马弗炉,加热速度大幅提高. 同时,微波灰化消解用酸量也非常小,既节约了酸的使用量,又减少了赶酸过程对环境的污染. 微波灰化消解法在元素检测前处理中主要应用于油料油品[1-5]、塑料 [6-7]、傣药[8]、食用菌[9]、小麦淀粉[10-11]、电泳材料[12]等样品.钙、磷都是人体必须的营养元素. 在人体吸收代谢过程中,钙和磷会相互影响. 根据GB 10765—2021《食品安全国家标准婴儿配方食品》[13]和GB 10767—2021《食品安全国家标准幼儿配方食品》[14]要求,钙磷元素比值范围分别为1∶1~2∶1和1.2∶1~2∶1,如果婴幼儿乳粉中钙磷比例失衡,婴幼儿对钙的有效吸收就会降低,造成膳食中钙营养元素的相对缺乏,影响骨骼和牙齿的发育,因此对婴幼儿乳粉中钙、磷元素进行检测十分必要.目前婴幼儿乳粉前处理方法主要有微波消解[13]、干法灰化[14]、高压罐消解[15]和湿法消解[16]. 国内未见微波灰化法在乳粉前处理中的应用研究. 由于乳粉基质比较复杂,添加物质较多,用传统的前处理方法对乳粉进行消解,有消解时间长、使用酸量大等不足. 本文以微波灰化为前处理方法,结合电感耦合等离子体发射光谱仪(ICP-OES)检测婴幼儿乳粉中钙、磷元素的含量,建立一种用时短、用酸量少的测定乳粉中钙、磷元素含量的检测方法.1 试验部分1.1 仪器与试剂电感耦合等离子体发射光谱仪(720型,安捷伦科技,美国),微波灰化仪(CEM,培安科技,美国),电子天平(Sartorius,塞多利斯公司,德国)(感量:0.001 g),瓷坩埚(50 mL). 硝酸(默克,优级纯),钙、磷标准溶液1 000 mg/L(中国计量科学研究院). 试验过程中所使用婴幼儿乳粉均购自超市,样品编号1、2、5样品为婴幼儿1段乳粉,样品编号3、4为纯奶粉,样品编号6为婴幼儿2段乳粉,样品编号7样品为婴幼儿3段乳粉. 试验过程中使用水均为去离子水. 所有使用的器具使用前均经20%硝酸浸泡过夜.1.2 试验方法1.2.1 标准溶液配制分别吸取钙、磷标准溶液1.0、2.0、3.0、4.0、5.0 mL于100.0 mL容量瓶中,使用2%硝酸定容至刻度,所配制溶液质量浓度分别为10、20、30、40、50 mg/L.硝酸溶液(硝酸∶水体积比为1∶1)配制:量取100 mL硝酸加入至100 mL去离子水中,混合均匀.1.2.2 试验方案在瓷坩埚中称量0.500 g乳粉,设定微波灰化程序进行试验,灰化完成后待微波灰化炉温冷却至150 ℃以下取出坩埚,晾至室温,用2.0 mL硝酸溶液(硝酸∶水体积比为1∶1)溶解灰分,将溶液转移至100.0 mL容量瓶中,用水清洗瓷坩埚,将清洗液转移至容量瓶中,用去离子水定容至刻度,混合均匀后进行钙、磷元素含量测定.1.3 ICP-OES仪器条件ICP-OES检测条件:功率1.2 kW,等离子体气气体流量:15.0 L/min,辅助器流量:1.50 L/min,雾化器流量:0.75 L/min,读数时间:1 s,进样时间:15 s,稳定时间:15 s. 各元素检测波长分别为钙317.933 nm、磷213.618 nm.1.4 微波灰化条件优化方案采用正交试验法对微波灰化条件进行优化,选取4因素4水平正交试验表,因素和水平如表1所列.表 1 正交试验的因素和水平Table 1 Factors and levels of orthogonal test因素因素A(灰化温度)/℃因素B(灰化时间)/min因素C(碳化温度)/℃因素D(碳化时间)/min 水平1450152002水平2500302504水平3550603008水平46009035012408分析测试技术与仪器第 29 卷2 结果与讨论2.1 微波灰化参数优化采用正交试验法对微波灰化的各个参数进行优化. 正交试验方案及结果如表2所列,正交试验结果分析如表3所列.从表3可以看出,磷元素4个因素极差从大到小的顺序为:A>C>B>D,钙元素4个因素极差从大到小的顺序为:A>B>C>D,因此灰化温度在整个灰化过程中起到重要的作用,碳化时间因素影响最小.2.1.1 微波灰化温度的优化正交试验因素的极差结果越大,代表该因素在试验条件中影响较大. 从正交试验极差分析结果可以看出,微波灰化温度极差最大,是影响灰化的最主要因素. 将微波灰化温度各个水平对应的k值为纵坐标,灰化温度为横坐标作因素水平图,如图1(a)所示. 从图1(a)可以看出,当灰化温度达到500 ℃时,钙和磷随着微波灰化温度的提高,所得到的含量没有明显的增加. 钙、磷两种元素最佳微波灰化温度虽然有所差别,但是差别不大. 综合以上结果,选择500 ℃作为微波灰化的最优温度.2.1.2 微波碳化温度的优化从表3可以看出,碳化温度是灰化效果的次主要因素. 碳化过程是将待处理的样品置于低温下使表 2 微波灰化正交试验方案及试验结果Table 2 Orthogonal test programs and results ofmicrowave ashing方案编号试验方案试验结果/(mg/kg)灰化温度/℃灰化时间/min碳化温度/℃碳化时间/min磷钙1450152002 2 605 3 514 2500153508 2 489 3 338 35501525012 2 545 3 411 4600153004 2 638 3 574 54503035012 2 199 2 928 6500302004 2 625 3 532 7550303002 2 615 3 504 8600302508 2 617 3 513 9450602504 2 490 3 334 105006030012 2 710 3 645 11550602008 2 542 3 414 12600603502 2 545 3 451 134******** 2 544 3 392 14500902502 2 650 3 565 155******** 2 721 3 664 166009020012 2 636 3 625表 3 灰化参数优化正交试验结果分析Table 3 Results analysis of orthogonal test/(mg/kg)元素 因素A因素B因素C因素D元素 因素A因素B因素C因素D 磷K19 83810 27710 40810 415钙K113 16813 83714 08514 034 K210 4741005610 30210 474K214 08013 47713 82314 104K310 4231028710 50710 192K313 99313 84414 11513 657K410 43610 5519 95410 090K414 16314 24613 38113 609k1 2 459 2 569 2 602 2 604k1 3 292 3 459 3 521 3 509k2 2 618 2 514 2 576 2 619k2 3 520 3 369 3 456 3 526k3 2 606 2 572 2 627 2 548k3 3 498 3 461 3 529 3 414k4 2 609 2 638 2 488 2 522k4 3 541 3 562 3 345 3 402极差159********极差249193184124极差顺序:A>C>B>D极差顺序:A>B>C>D最优水平:A2B4C3D2最优水平:A4B4C3D2注:K1、K2、K3、K4表示任意列上水平1、水平2、水平3、水平4所对应的试验结果之和;k1、k2、k3、k4表示水平1、水平2、水平3、水平4对应试验结果均值第 4 期陈丽梅,等:微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷409其碳化,减少因温度上升过快而使得样品灰分的挥发. 以微波灰化碳化温度各个水平对应k 值为纵坐标,碳化温度为横坐标作因素水平图,如图1(b )所示.从图1(b )可以看出,过高的碳化温度并不利于微波灰化的结果. 随着碳化温度的提高,样品碳化过程过快,使得元素随着碳化的烟雾挥出,造成了元素含量的损失. 当碳化温度为300 ℃时,钙和磷含量均达到最佳水平. 因此选择最佳的碳化温度为300 ℃.2.1.3 微波灰化时间的优化以微波灰化时间各个水平对应k 值为纵坐标,微波灰化时间为横坐标作因素水平图,如图1(c )所示.从图1(c )中可看到并没有最优的灰化时间点出现,因此对微波灰化时间进行了单点优化,结果如图1(d)所示. 从图1(d) 中可以看出,当灰化时间达到90 min 后,延长灰化时间对于消解并没有明显的改善,综合考虑各元素的灰化时间,选择最优的灰化时间为90 min.2.1.4 碳化时间的优化以碳化时间各个水平对应k 值为纵坐标,碳化时间为横坐标作因素水平图,结果如图2所示. 从图2可以看出,当碳化时间达到4 min 时,钙和磷的含量水平达到最优,因此所选碳化时间为4 min.2.1.5 称样量的优化通过正交试验结果,选择最佳微波灰化条件:微波灰化温度500 ℃,灰化时间90 min ,碳化温度300 ℃,碳化时间4 min. 在最优的条件下对不同称样量(0.2、0.5、1.0、2.0、3.0 g )样品进行前处理,采用ICP-OES 对其含量进行检测,以样品含量为纵坐标,样品称样量为横坐标作图3. 当称样量达到2.0 g 时,婴幼儿乳粉出现了灰化不完全的情况,定容样品中含有黑色沉淀. 从图3也可以看出,当称2 0002 5003 0003 5004 000元素质量分数/(m g /k g )T /℃1 5002 0002 5003 0003 5004 000T /℃元素质量分数/(m g /k g )1 5002 0002 5003 0003 5004 000元素质量分数/(mg /k g )t /min2 0002 5003 0003 5004 0004 5005 000元素质量分数/(m g /k g )t /min图1 (a )灰化温度、(b )碳化温度、(c )微波灰化时间的因素水平图、(d )微波灰化时间的单点优化Fig. 1 Factor level diagrams of (a) microwave ashing temperatures, (b) microwave carbonization temperatures and(c) microwave ashing times, (d) optimization of microwave ashing times1 5002 0002 5003 0003 5004 000元素质量分数/(m g /k g )t /min图2 碳化时间的因素水平图Fig. 2 Factor level diagram of microwave carbonizationtimes410分析测试技术与仪器第 29 卷样量达到2.0 g 时,检测到的样品含量出现下降的趋势,这是由于样品称样量过多时,样品没有被完全灰化,待测元素无法完全转移到溶液中,造成检测含量降低. 因此最佳称样量应小于2.0 g.2.2 各元素仪器方法学考察采用外标法对各元素进行检测,以元素浓度(X )为横坐标,元素在ICP-OES 检测强度(Y )为纵坐标拟合线性方程,得到线性方程和相对标准偏差(RSD ). 各元素检出限取3倍样品空白标准偏差(n =11)计算,定量限取10倍样品空白标准偏差(n =11)计算. 所得结果如表4所列.表 4 线性方程、检出限和定量限Table 4 Linear regression equations, limits of detection and limits of quantitation元素线性方程线性范围/(mg/L )相关系数RSD/%检出限/(mg/L )定量限/(mg/L )钙Y =37 341.809 + 55 064.512X 0~500.9990.860.023 70.079磷Y =602.582 + 1 742.811X0~500.9990.750.022 50.0752.3 加标回收试验在婴幼儿乳粉中添加标准溶液,采用最优灰化条件进行样品处理后采用ICP-OES 进行检测,结果如表5所列. 从表5可以看出,磷元素加标回收率为86%~104%,钙元素加标回收率为87%~96%. 磷和钙元素6次加标回收率的RSD 分别为2.5%~7.0%,3.9%~10.0%. 加标回收率结果能够满足日常检测要求.表 5 加标回收率Table 5 Results of recovery元素背景/(mg/kg)添加质量分数/(mg/kg)测得质量分数/(mg/kg)加标回收率/%RSD/(%,n =6)磷2 582500 3 0911027.01 000 3 623104 4.22 0004 30386 2.5钙4 1771 0005 0478710.02 0006 01792 4.73 0007 057963.92.4 实际样品的检测采用所建立的方法对市场采购的婴幼儿乳粉进行钙、磷元素含量测定,测定结果如表6所列. 从表中可以看出,所检测的样品编号1、2、5号样品钙磷比值分别为1.4、1.6、1.6,符合GB 10765—2021《食品安全国家标准 婴儿配方食品》[13]要求. 样品编号3、4 号样品是纯奶粉和甜奶粉,钙磷比值分别为1.2和1.1. 样品编号6、7号样品比值分别为1.7、1.3,符合GB 10767—2021《食品安全国家标准 幼儿配方食品》[14]要求.2.5 微波灰化与其他消解方法的比较将微波灰化法与其他前处理方法消解体系和所用时间进行比较,结果如表7所列. 微波灰化前处理方法的精密度和回收率能够满足日常检测的需求. 与干法灰化相比,由于微波的使用,大大增加了加热效率,从而使在进行婴幼儿乳粉前处理过程m /g1 5002 0002 5003 0003 5004 0004 500元素质量分数/(m g /k g )图3 样品称样量的选择Fig. 3 Optimization of sample weights第 4 期陈丽梅,等:微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷411中所需要的灰化时间更短,总体处理时间与微波消解相当. 微波灰化前处理只需要在灰化完成后用少量酸溶解样品,因此用酸量与湿法消解相比更少.说明微波灰化用于婴幼儿乳粉中钙、磷检测的前处理,所用时间少,消解所用到的酸的种类和剂量也很少,减少了酸的使用对于实验环境和实验人员的危害.3 结论采用微波灰化对婴幼儿乳粉中钙、磷元素进行样品前处理,相比微波消解方法,具有用时短、用酸量少、消解效果好、不需要进行赶酸处理等优势. 与干法灰化和湿法消解相比大大减少了样品处理时间. 采用微波灰化与ICP-OES 结合对婴幼儿乳粉中重要的指标元素钙、磷元素进行检测,是一种快速、环保、准确度高的方法,在婴幼儿乳粉质量控制中有很好的应用价值.参考文献:俞晔, 乙小娟, 刘一军. 微波灰化-原子荧光光谱法测定植物油中砷[J ]. 现代科学仪器,2002(6):48-50.[YU Ye, YI Xiaojuan, LIU Yijun. Determination of arsenic in vegetable oil by AFS method using mi-crowave ashing [J ]. Modern Scientific Instruments ,2002 (6):48-50.][ 1 ]王楼明, 叶锐钧, 林燕奎, 等. 微波灰化-氢化物发生-原子荧光光谱法测定原油和燃料油中的铅和砷[J ].[ 2 ]化学分析计量,2009,18(2):33-36. [WANG Lou ming, YE Ruijun, LIN Yankui, et al. Determination of lead and arsenic in crude oil and fuel oil by mi-crowave ashing hydride generation atomic fluores-cence spectrometry [J ]. Chemical Analysis and Meter-age ,2009,18 (2):33-36.]徐晓霞, 张海峰, 谭智毅, 等. 微波灰化-电感耦合等离子体原子发射光谱法测定石油焦中铁[J ]. 检验检疫学刊,2015,25(3):21-24. [XU Xiaoxia,ZHANG Haifeng, TAN Zhiyi, et al. Determination of iron in petroleum coke by ICP-AES with microwave ash technology [J ]. Journal of Inspection and Quarant-ine ,2015,25 (3):21-24.][ 3 ]荣丽丽, 孙玲, 王磊, 等. 微波灰化等离子发射光谱法测定渣油中的铁、镍和钒[J ]. 精细石油化工进展,2014,15(1):56-58. [RONG Lili, SUN Ling, WANG Lei, et al. Determination of iron, nickel and vanadium contents in residual oil with microwave ashing tech-nique and inductively coupled plasma atom emission spectrometry [J ]. Advances in Fine Petrochemicals ,2014,15 (1):56-58.][ 4 ]胡健. 微波灰化样品-电感耦合等离子体原子发射光谱法测定原油中微量金属元素[J ]. 化学工程与装备,2021(11):205-206. [HU Jian. ICP-OES De-termination of trace amount of metal elements in crude oil with microwave assisted ashing of sample [J ].Chemical Engineering and Equipment ,2021 (11):205-206.][ 5 ]王鹏, 沈良君, 李啸峰, 等. 微波灰化-ICP 法测定塑料中钡、镉、钴、铜含量[J ]. 广州化工,2013,41(15):[ 6 ]表 6 实际样品的检测Table 6 Detection of samples/(mg/kg)元素样品编号1样品编号2样品编号3样品编号4样品编号5样品编号6样品编号7磷 2 968 3 0958 109 4 760 2 431 3 793 5 964钙4 2174 9459 5315 0353 9706 3587 973表 7 微波灰化与其他前处理方法比较Table 7 Comparison between microwave ashing and other pretreatment methods方法体系所用时间文献微波灰化 2.0 mL 硝酸溶液(硝酸∶水体积比1∶1)90 min 本方法微波消解 5.0 mL 硝酸+1 mL 双氧水约2 h [15]干法灰化 2.0 mL 硝酸溶液(硝酸∶水体积比1∶1)4~5 h [16]高压消解 5.0 mL 硝酸+1.0 mL 双氧水 3 h [17]湿法消解10 mL 硝酸∶高氯酸(体积比为4∶1)4~5 h[18]412分析测试技术与仪器第 29 卷129-131. [WANG Peng, SHEN Liangjun, LI Xiaofeng, et al. Determination of barium, cadmium,cobalt, copper content in plastics by ICP-OES after mi-crowave ashing [J ]. Guangzhou Chemical Industry ,2013,41 (15):129-131.]张树全. 微波灰化-等离子发射光谱法测定茂金属聚乙烯中的钛、铝、锆[J ]. 橡塑技术与装备,2017,43(6):44-46. [ZHANG Shuquan. Determination of Ti, Al and Zr in metallocene polyethylene with mi-crowave ashing technique and inductively coupled plasmaemissionspectrometry [J ].ChinaRubber/Plastics Technology and Equipment ,2017,43(6):44-46.][ 7 ]夏从芳, 张龙旺, 白玮, 等. 微波灰化-ICP-MS 法测定傣药肾叶山蚂蝗中的金属元素[J ]. 江苏农业科学,2013,41(11):342-344. [XIA Congfang, ZHANG Longwang, BAI Wei, et al. Determination of metal elements in Desmodium reniforme by microwave ash-ing-ICP-MS [J ]. Jiangsu Agricultural Sciences ,2013,41 (11):342-344.][ 8 ]倪张林, 汤富彬, 屈明华, 等. 微波灰化-液相色谱-电感耦合等离子体质谱联用测定干食用菌中的三价铬和六价铬[J ]. 色谱,2014,32(2):174-178. [NI Zhanglin, TANG Fubin, QU Minghua, et al. Determin-ation of trivalent chromium and hexavalent chromium in dried edible fungi by microwave ashing-liquid chro-matography with inductively coupled plasma mass spectrometry [J ]. Chinese Journal of Chromatography ,2014,32 (2):174-178.][ 9 ]张慧, 夏拥军. 微波灰化-氢化物发生-原子荧光光谱法测定出口小麦淀粉中痕量铅[J ]. 光谱实验室,2005,22(3):559-563. [ZHANG Hui, XIA Yongjun.Determination of trace lead in exported wheat starch by microwave ashing-hydride generation-atomic fluor-escence spectrometry [J ]. Chinese Journal of Spectro-scopy Laboratory ,2005,22 (3):559-563.][ 10 ]李旭, 吴维吉, 刘佳, 等. 微波灰化电感耦合等离子体质谱法测定小麦中6种金属元素含量[J ]. 食品安全质量检测学报,2019,10(4):866-869. [LI Xu, WU Weiji, LIU Jia, et al. Determination of 6 kinds of met-al elements in wheat by microwave ashing and induct-ively coupled plasma-mass spectrometry [J ]. Journal[ 11 ]of Food Safety & Quality ,2019,10 (4):866-869.]吴志刚, 曹璨. 微波灰化-电感耦合等离子体质谱法测定电泳涂料中15种金属元素[J ]. 化学分析计量,2023,32(1):6-10. [WU Zhigang, CAO Can. Determ-ination of fifteen elements in electrophoretic coating by microwave ashing-inductively coupled plasma mass spectrometry [J ]. Chemical Analysis and Meterage ,2023,32 (1):6-10.][ 12 ]国家卫生健康委员会, 国家市场监督管理总局. 食品安全国家标准 婴儿配方食品: GB 10765—2021[S ]. 北京: 中国标准出版社, 2021.[ 13 ]国家卫生健康委员会, 国家市场监督管理总局. 食品安全国家标准 幼儿配方食品: GB 10767—2021[S ]. 北京: 中国标准出版社, 2021.[ 14 ]马征, 常雅宁. 微波消解-ICP-OES 法同时测定婴幼儿奶粉中的14种无机元素[J ]. 中国乳品工业,2017,45(1):43-46, 60. [MA Zheng, CHANG Yaning. De-termination of 14 trace elements in infant formula milk powder by microwave digestion-ICP-OES [J ]. China Dairy Industry ,2017,45 (1):43-46, 60.][ 15 ]宋龙波, 赵龙刚, 赵延伟, 等. 火焰原子吸收光谱法测定婴幼儿奶粉中铁、锌元素含量[J ]. 安徽农业科学,2012,40(33):16374-16376. [SONG Longbo, ZHAO Longgang, ZHAO Yanwei, et al. Determination of Fe and Zn in infant formula milk power by flame atomic absorption spectrometry [J ]. Journal of Anhui Agricul-tural Sciences ,2012,40 (33):16374-16376.][ 16 ]吴育廉. 高压密封湿法消解-火焰原子吸收光谱法测定婴儿配方奶粉中铁和锌[J ]. 微量元素与健康研究,2011,28(3):49-50. [WU Yulian. Digestion with high pressure airproof pot - Determined of Fe and Zn in Baby formula by using flame atomic absorption spectrometry [J ]. Studies of Trace Elements and Health ,2011,28 (3):49-50.][ 17 ]陈晓, 张晓文, 赵广才. 三种不同前处理方法对标准奶粉中锰含量测定的影响[J ]. 广东微量元素科学,2015,22(11):27-29. [CHEN Xiao, ZHANG Xiao wen, ZHAO Guangcai, et al. The effect of manganese contentdeterminationbythreepretreatmentmethods [J ]. Guangdong Trace Element Science ,2015,22 (11):27-29.][ 18 ]第 4 期陈丽梅,等:微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷413。

V_(2)O_(5)g

V_(2)O_(5)g

第34卷第1期2021年2月Vol.34No.1Feb.2021投稿网址: 石油化工高等学校学报JOURNAL OF PETROCHEMICAL UNIVERSITIESV2O5/g⁃C3N4催化剂的制备及其模拟油中硫化物的脱除张豪,李秀萍,赵荣祥(辽宁石油化工大学石油化工学院,辽宁抚顺113001)摘要:以三聚氰胺、偏钒酸铵、硼酸为前驱体,通过煅烧法制备V2O5/g⁃C3N4催化剂。

采用XRD、FT⁃IR、XPS、SEM和BET等技术对催化剂的结构与形貌进行表征。

以V2O5/g⁃C3N4为催化剂,乙腈为萃取剂,H2O2为氧化剂对模拟油中二苯并噻吩(DBT)的脱除进行考察。

探究了反应温度、催化剂质量、萃取剂体积、n(H2O2)/n(S)以及不同硫化物等因素对脱硫效果的影响。

在模拟油体积为5.0mL、萃取剂乙腈体积为3.0mL、n(H2O2)/n(S)=8、催化剂质量为0.02g、反应温度为30℃和反应时间为60min的最佳条件下,DBT的脱除率达到91.9%,经过5次催化剂再生后脱硫率仍可以达到85.7%。

关键词:V2O5/g⁃C3N4;氧化脱硫;二苯并噻吩;三聚氰胺中图分类号:TE624文献标志码:A doi:10.3969/j.issn.1006⁃396X.2021.01.002Preparation of V2O5/g⁃C3N4Catalyst and Desulfurization Ability in Model OilZhang Hao,Li Xiuping,Zhao Rongxiang(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun Liaoning113001,China)Abstract:The V2O5/g⁃C3N4catalyst was prepared by calcination method,using melamine,ammonium metavanadate,boric acid as precursors and methanol as solvent.The structure and morphology of the catalyst were characterized by X⁃Ray Diffraction(XRD), Fourier transform infrared spectroscopy(FT⁃IR),X⁃ray photoelectron spectroscopy(XPS),scanning tunneling microscope(SEM) and brunauer⁃emmett⁃teller(BET).The desulfurization ability of dibenzothiophene(DBT)in model oil was investigated using V2O5/g⁃C3N4as catalyst,acetonitrile as extractant and H2O2as oxidant.The effects of reaction temperature,amount of catalyst and extractant,n(H2O2)/n(S)molar ratio,and different sulfides on desulfurization rate were investigated.Under the optimum conditions: 5.0mL model oil,3.0mL acetonitrile,n(H2O2)/n(DBT)=8,0.02g of catalyst,temperature was30℃and reaction time was60min, the desulfurization rate of DBT can reach91.9%,which can also keep at a higher value at85.7%after5times of catalyst regeneration. Keywords:V2O5/g⁃C3N4;Oxidative desulfurization;Dibenzothiophene(DBT);Melamine随着汽车工业的迅速发展,燃料油燃烧产生的硫化物对环境的污染越来越严重[1⁃2]。

碳点-水凝胶 电催化 铀酰离子-概述说明以及解释

碳点-水凝胶 电催化 铀酰离子-概述说明以及解释

碳点-水凝胶电催化铀酰离子-概述说明以及解释1.引言1.1 概述概述部分的内容可以如下所示:在当前环境保护和能源开发的背景下,研究人员越来越关注使用新材料和技术来解决能源和环境问题。

碳点-水凝胶和电催化技术作为近年来新兴的研究领域备受瞩目。

碳点-水凝胶是一种由碳点和水凝胶相结合形成的新型材料,其独特的结构和性质使其在催化、能源转化和环境治理等领域展现出巨大的潜力。

碳点作为一种纳米级碳材料,具有较大的比表面积和优异的光电性能,可用于催化反应和能源转化。

而水凝胶则是一种含水网络结构材料,具有良好的柔韧性和高度吸水性,可用于吸附和固定其他物质。

通过将碳点与水凝胶相结合,人们可以制备出具有双重功能的新型材料,既保留了碳点的优点,又增加了水凝胶的特性,为各种应用提供了更多可能性。

另一方面,电催化技术是利用电化学方法来催化化学反应的一种方法。

通过引入电流使反应发生,并在电极表面引入催化剂,可以实现高效的催化反应。

与传统的热催化相比,电催化技术具有能耗低、反应选择性高和环境友好等优势。

因此,电催化技术在减少能源消耗和污染物排放方面具有重要的应用潜力。

铀酰离子是一种在核能领域具有重要意义的离子物种。

研究铀酰离子的电催化性质对于核能的开发和利用具有重要意义。

近年来,研究人员发现碳点-水凝胶在铀酰离子电催化中展示出优异的性能表现,这使其成为相关领域的研究热点。

本文将对碳点-水凝胶、电催化技术和铀酰离子的研究进行综述和分析,以期深入了解这些领域的最新进展和应用前景。

通过对相关文献和实验结果的综合分析,本文旨在为读者提供一个全面的概述,以便更好地理解碳点-水凝胶、电催化和铀酰离子研究的重要性和应用前景。

文章结构是指整篇文章按照一定的组织方式和逻辑结构来安排的,以便读者能够更好地理解和掌握文章的主题和内容。

本文按照以下结构展开:1. 引言1.1 概述在本节中,将简要介绍碳点-水凝胶和铀酰离子等关键概念,并说明它们在电催化中的重要性。

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Corona-induced electrohydrodynamic instabilities in low conducting liquidsF.Vega,A.T.Pe´rezAbstract The rose-window electrohydrodynamic(EHD) instability has been observed when a perpendicularfield with an additional unipolar ion injection is applied onto a low conducting liquid surface.This instability has a characteristic pattern with cellsfive to10times greater than those observed in volume instabilities caused by unipolar injection.We have used corona discharge from a metallic point to perform some measurements of the rose-window instability in low conducting liquids.The results are compared to the linear theoretical criterion for an ohmic liquid.They confirmed that the minimum voltage for this instability is much lower than that for the inter-facial instability in high conducting liquids.This was predicted theoretically in the dependence of the critical voltage as a function of the non-dimensional conductivity. It is shown that in a non-ohmic liquid the rose window appears as a secondary instability after the volume instability.1IntroductionThe stability of a perpendicular-fieldfluid interface is a classical problem in electrohydrodynamics.One of the instabilities associated with this problem is the unipolar-injection induced instability.Although corona discharge is a very well-known experimental technique,it has not been applied extensively to produce liquid motion.There is only some descriptive work on the EHD instabilities induced by unipolar charge injection using the corona discharge,such as in the works by Herrick(1974),Ahmed El-Haddad et al.(1980),Malraison and Atten(1991).The corona discharge occurs when a gas in the vicinity of an electrode loses its electrical neutrality due to a very high non-homogeneous electricfield.A non-homogeneous electricfield can be obtained,for example,in a tip–plane configuration.If the DC voltage applied to the tip is high enough(above a certain threshold)the ionisation can sustain a continuous discharge(corona)that produces a stationary space charge distribution.Actually,corona discharge is a rather complex phenomenon(Hish and Oskam1978),depending on many physical and geomet-rical parameters.However,for the problem to be treated in this work,the EHD instability at a two-fluid interface,the corona discharge is used merely as a continuous source of ions,and the detailed processes involved in the discharge do not have any significant influence.Corona discharge provides a technique to reproduce experimentally the EHD instabilities in liquids under a perpendicularfield and steady unipolar charge injection that appear in the theoretical models developed in the works by Atten and Moreau(1972),Lacroix et al.(1975), Atten and Lacroix(1979),Schneider and Watson(1970), Koulova-Nenova and Atten(1997),Koulova-Nenova and Atten(1998),Atten and Koulova-Nenova(1999)and Vega and Pe´rez(2002).In these works the non-ohmic conduc-tion is supposed to be a consequence of the presence of a space charge source(an injecting electrode).Actually,not only injection itself can contribute to the appearance of a space charge in the dielectricfluid.In the case of an insulating liquid other processes due to the existence of a residual conductivity,like recombination and dissociation reactions in the bulk of thefluid,may have an influence and modify the EHD instability criteria(Atten1975; Pontiga et al.1995;Pontiga and Castellanos2000).This residual conductivity could be one of the reasons for the disagreement between theory and experiments,and,con-sequently,some effort has been done experimentally to eliminate its effect(Lacroix et al.1975;Atten and Lacroix 1979).However,it seems that the disagreement comes from the difficulty of reproducing exactly in an experi-mental set-up all the theoretical assumptions made in the resolution of the problem of unipolar injection.For a general review and references of the unipolar injection problem in electrohydrodynamics,see Castellanos et al. (1998).In this work,we study experimentally the electrohy-drodynamic instabilities induced by corona discharge in very low conducting liquids.First of all,as the ion density in air is low enough(n0~400cm)3)the residual conduc-tivity C0(Pontiga and Castellanos2000)is small and the Experiments in Fluids34(2003)726–735DOI10.1007/s00348-003-0616-y726Received:4February2002/Accepted:9December2002Published online:14May2003ÓSpringer-Verlag2003F.Vega(&),A.T.Pe´rezDepto.Electro´nica y Electromagnetismo,Facultad de Fı´sica,Universidad de Sevilla,Avda.Reina Mercedes,s/n.41012,Sevilla,SpainE-mail:fvega@us.esThe authors wish to thank Professor Francisco Pontiga forfruitful discussions and‘‘Taller de la Facultad de Fı´sica’’of theUniversity of Seville for technical assistance.This work has beencarried out withfinancial support from the Spanish Government(Ministerio de Ciencia y Tecnolog,MCYT)under researchproject BFM2000-1056effects of recombination reactions can be neglected:C0=en0L2/(e0V)~5Æ10)10>1,where L is the air layer thickness and V the applied electric potential(around1to 10kV in the measurements).We consider two different cases:liquids in ohmic and non-ohmic regimes.In both cases the liquid layer is in contact with the air,and the air is in contact with the injecting electrode.When a charge injection is exerted into the air layer the electricfield pushes down the space charge towards the interface.If the liquid is in non-ohmic regime this space charge penetrates through the interface and induces electric forces in bulk of the liquid that can produce the classic EHD convective instability.This instability has a characteristic wavelength of the order of the liquid layer thickness(Atten and Moreau1972).Lacroix et al.(1975)and Atten and Lacroix(1979)studied the convective instability in an experimental set-up where the ions are directly injected into an insulating liquid layer with the use of an electro-dialytic membrane that serves as a rigid injecting electrode (Felici and Tobazeon1981).Watson et al.(1970)repro-duced this instability experimentally with the use of an electron beam that injects space charge into an insulating liquid layer in a vacuum.The theoretical model that clo-sely approaches this experiment can be found in the work by Schneider and Watson(1970).The injecting electrode here is the liquid free surface.The electron-beam charge injection technique is described by Watson and Clancy (1965).The corona discharge from a tip produces the same convective instability in very low conducting liquids as was demonstrated by Malraison and Atten(1991).We have reproduced this experiment and some of the resulting measurements concerning this instability are presented here.But another possible and much less known instability in a perpendicular-field unipolar injection problem is the rose-window instability,which is a phenomenon that until now has been observed only in low conducting liquids in contact with air(Pe´rez1997)and subjected to corona discharge.Other authors(Herrick1974;Ahmed El-Haddad et al.1980)have observed similar patterns, but their descriptions do not help to clarify under what experimental conditions and in what kind of liquids they are observable.A theoretical description of the instability mechanism in the case of an ohmic liquid was carried out by Vega and Pe´rez(2002).It is clear that in the air the effects of a residual conductivity are negligible and in this theoretical analysis they have not been taken into account.Under unipolar charge injection and provided the liquid conductivity is low enough an electric pressure of the same sign of the applied electricfield is exerted onto the interface.This electric pressure can produce a surface deformation above a certain threshold.The perturbation is kept because the current density(and, correspondingly,the electric pressure)is higher in the thinner areas of the deformed interface(Vega and Pe´rez 1999b).The deformation has a characteristic wavelength typically aboutfive to10times larger than in the con-vective instability.Therefore the rose-window instability can be grouped into the type of interfacial instabilities, like those in an ohmic/ohmic interface(Melcher1963; Melcher and Smith1969;Chu et al.1989;Ne´ron de Surgy et al.1993;Gonza´lez et al.1994;Ne´ron de Surgy1995;El-Dib1999),as they are due to the destabilising effect ofthe electric pressure over thefluid interface,but unlikethe cases considered by these authors,it is characterisedby the existence of a space charge distribution in one orboth sides of the interface.We present here a set of measurements for the rose-window instability.We thinkthey are strong experimental evidence of one of thepossible interfacial EHD instability mechanisms in a perpendicular-field non-ohmic/ohmic interface(Vegaand Pe´rez2002).The measurements we performed also provide evidence that corona discharge is a valid experimental technique for obtaining the rose-windowand the convective EHD instabilities in air/liquid inter-faces.The two experimental set-ups that are used in this workare described in Sect.2.With one of the experimental set-ups we have tried to approach the plane geometry modelin order to compare the experimental results with thetheory.In Sect.3the results are presented,together with aset of photographs of the instabilities.A comparison with theory(Vega and Pe´rez2002)is provided in Sect.4.Finally we present our conclusions in Sect.5.2Experimental set-upIn the experimental set-up we place a metallic tip(tung-sten)of about10l m radius above the centre of a circularplane electrode of4.5cm diameter.The electrode is a transparent glass with a thin conducting coating.The li-quid is placed over this plane electrode.A mirror belowthe transparent electrode is used to deviate the image ofthe liquid surface to a camera system that amplifies it todetect the deformation.A ring of acrylic glass prevents the leakage of the liquid(see Fig.1a).This acrylic glass sup-port isfixed onto a table(Melles Griot model,Voisins Le Bretonneux,France)through an acrylic glass structure of15cm height(Fig.1b).The electrode is connected to an electrometer(model6512,Keithley Instruments,Cleve-land,Ohio,USA)in order to measure the electric current through the liquid.The tip is connected to a high voltage source(model RHR40PN120/OV/FG,Spellman HighVoltage Electronics,Hauppauge,N.Y.,USA).The ionsfrom the corona discharge reach the plane electrode byelectric repulsion from the tip and exert an electric pres-sure over the liquid.This is called the‘‘tip–plane set-up’’.The hyperbolic geometry of the electricfield in a tip–planeconfiguration(Coelho and Debeau1971)makes it difficultto compare with the plane geometry models used in a theoretical analysis of the problem.Besides,the spacecharge distribution caused by corona discharge in atip–plane configuration is far from homogeneous(Atten1996;Giacometti1987).This is why a metallic gridcan be optionally interposed between the tip and thecircular electrode.The grid we used is square-shaped with copper wires of a=0.25mm diameter and a separation ofb=1.5mm between the wire centres.This grid is connectedto another high voltage source(model610C,Trek Inc., Medina,N.Y.,USA),which provides a more homogeneous electricfield and corona distribution over the liquid sur-face.The electrode is required to be transparent in order727to have a clear image from below if the metallic grid is used.The complete set-up,called ‘‘triode’’(three-electrode system)is shown in Fig.1b.The grid is held between two other acrylic glass rings that are screwed to the first one,and then the set of acrylic glass rings,transparent elec-trode and grid are firmly fixed.We can also vary both thetip–plane distance,as the tip is held by a metallic rod fixed perpendicularly to a moving plane,and the grid–plane distance,as we have a set of acrylic glass rings with dif-ferent thicknesses.The tip–plane and grid–plane distances are of the order of 1cm.Figure 2is a plot of the current that arrives at the plate as a function of the grid voltage for different tip voltages,in the absence of liquid.When the grid voltage is zero,no current reaches the plane electrode.(Actually,there is a current caused by corona wind,see the work by Giaco-metti and Sine´zio (1990),but it is too small to produce instability.)If we raise the grid voltage the current grows and,at the same time,the electric field over the liquid is higher.When the grid voltage is high enough to decrease the corona current coming from the tip,the current into the liquid starts to decrease.With the tip–grid–plane configuration it is possible to apply to the liquid the same electric field with different electric currents,by varying the tip voltage.We have used extensively three liquids.Under our experimental conditions and because of their initial con-ductivities,two of the liquids are in the ohmic regime (castor and corn oils)and the third one is in the non-ohmic regime (silicone oil).The properties of the liquids are represented in Table 1.These properties have been measured in our laboratory.Specifically,the conductivity has been measured with a conductivity meter IRLAB model LDTRP-2.We have performed measurements with several volumes of liquid to vary the liquid layer thickness that is typically of the order of 1mm.All measurements were performed in Seville,Spain,April–May (Figs.3,5,9,10,11,12,13,14,15,16)and November (Figs.4,6,7and Table 2)2001.Fig.1.a Scheme of the triode set-up.The tip-to-plane distance is p and the grid-to-plane distance is h .b The dimensions of the grid–planesystemFig.2.Electric current I that arrives at theplate as a function of the grid voltage V g (triode set-up)for different tip voltages V p .Distances are:between the tip and the grid p )h =3.0cm,and between the grid and the plate h =0.5cm.The electrode area in this series is A =1.96Æ10)3m 2Table 1.Physical properties of the liquids used in theexperiments,e is the relative electric permittivity and m is the kinematic viscosity Oile q (kg/m 3)m (m 2/s)K (m 2/Vs)r (W -1m -1)Silicone 2.7396050Æ10-65Æ10-106Æ10-13Castor 4.69958600Æ10-64Æ10-117Æ10-11Corn3.199055Æ10-64.5Æ10-101.9Æ10-117282.1Measurements The critical points were obtained by taking the voltage atthe first surface deformation.The deformation was ob-served through a photographic objective.We have notedthat the use of transparent electrodes makes visual observation equally as sensitive for detecting the insta-bility as other methods that we have designed (see,forexample,the work by Pe´rez (1997)).In the tip–plane set-up the tip voltage is raised until the instability starts.This value of the tip voltage is taken as the critical value.The liquid used in this set-up must be viscous enough toavoidFig.3.Rose-window instability.Critical grid voltages for liquids in the ohmic regime (castor oil and corn oil)as afunction of the tip voltage in a triode set-up,for several liquid layer thicknesses.Distances are:p )h =2.5cm,h =1.5cm.In all measurements,the electrode area is A =1.59Æ10)3m 2(diameter:4.5cm)Fig.4.Rose-window instability.Critical grid voltages as a function of the tipvoltage in a triode set-up,for several liquid layer thicknesses.Liquid:silicone oil (non-ohmic).Distances are:p )h =2.5cm,h =0.8cmFig.5.Rose-window instability.Criticalgrid voltages as a function of the electric current in a triode set-up,for several liquid layer thicknesses.Liquid:castor oil (ohmic).Distances are:p )h =2.5cm,h =1.5cmTable 2.Critical values of the current density in silicone oil(non-ohmic behaviour).Triode set-up.Tip–grid distance:3.5cm,grid–plane distance:0.8cm d (mm)I (l A)I(A)d 3(m)0.130.262 6.45Æ10–190.180.108 6.31Æ10–190.220.058 6.61Æ10–190.270.003 6.50Æ10–190.310.020 6.25Æ10–190.360.013 6.07Æ10–190.400.010 6.31Æ10–190.450.0076.31Æ10–19729the effects of the corona wind:if the viscosity is low,the surface of the liquid moves too much before the instability onset and it is not possible to study the instability from an initial static state.Some tests have been performed in low viscous liquids,like water,and the effect of the corona wind is to disturb the liquid surface,just below the tipcentre.In the case of the triode set-up (Vega and Pe´rez 1999a),the corona wind is largely suppressed by the grid.To take the critical points in the triode we fix the tip voltage and vary the grid voltage.The critical grid voltage is taken when the first surface deformation occurs,which happens always when the current is increasing with the grid voltage,if the tip voltage is high enough.The grid voltage controls,essentially,the electric field onto the liquid surface.The critical voltages for the rose-window instability in a triode set-up are shown in Figs.3and 4for the three different liquids.These critical grid voltages are plotted as a function of the tip–plane voltage.The critical voltages show a clear tendency to increase for thicker liquid layers.Also the critical grid voltages show a tendency to decrease with the tip voltage.This is a consequence of the fact that the current density reaching the liquid increases with the tip voltage.Then the electric pressure for equal gridvoltages increases with the tip voltage.This is in agreement with the tendencies shown in Figs.5and 6,where the critical grid voltages are plotted against the electric cur-rent.Although the dispersion of the electric current data is high because the current value is very sensitive to a grid voltage variation (a rough estimation from the experi-mental current curves shows that a typical error in the grid voltage of 50V induces an error of about 0.025l A in the current),it can be seen that the critical electric current decreases if the critical voltage increases.In the non-ohmic liquid it is also clear that the critical current increases if the liquid thickness decreases,which is not so evident in the ohmic liquid.In the case of a non-ohmic liquid,there are two critical values corresponding to the two possible instabilities:the convective instability and the rose-window instability.Among the three liquids used we have only seen convec-tive instability in silicone oil,providing in this case evi-dence of the existence of space charge in the volume of the liquid.The conduction regime of the liquid can be esti-mated as follows:the characteristic non-ohmic conduction time in silicone oil layer with d =1mm (see properties in Table 1)is d 2/K l V l ~10)6/(5Æ10)10Æ2Æ102)~10s (being V l the voltage drop through the liquid layer and K l the ion mobility in the liquid)and the charge relaxation time is higher:e l /r =2.73Æ8.85Æ10)12/(6Æ10)13)=40s (e l is thedielectric constant in the liquid)and then there is a net space charge in the bulk of the layer (besides,in this work d <2mm).A similar estimation in castor and corn oil gives charge relaxation times lower than the non-ohmiccon-Fig.6.Rose-window instability.Criticalgrid voltages as a function of the electric current in a triode set-up,for several liquid layer thicknesses.Liquid:silicone oil (non-ohmic).Distances are:p )h =2.5cm,h =1.5cmFig.7.Rose-window instability for verythin liquid layers in an ohmic liquid (castor oil)and in a non-ohmic liquid (silicone oil).In this plot V c is the tip voltage at which the instability is first observed,and d is the liquid layer thick-ness.In the case of castor oil the instability is observed as soon as the corona thresh-old is reached.Tip-to-plane distance p =3.0cm730duction characteristic time,which means that the electric conduction is ohmic,and no space charge can be supported.Theoretically,the behaviour of the rose-window insta-bility for small liquid thicknesses is expected to be very different in ohmic and non-ohmic liquids:while in ohmic liquids the critical voltage tends to a small value,in non-ohmic liquids it tends to infinity near a critical value d crit and down to this value the instability is absent.Then,the two types of conduction regimes are supposed to have an opposite behaviour for very thin liquid layers.This behaviour is found experimentally as shown in Fig.7where critical values for thin liquid layers in a tip–plane set-up have been plotted for silicone oil (non-ohmic)and castor oil (ohmic).Note that the tip critical voltage is plotted in the vertical axes in this figure.In this set-up there is no current below the corona threshold and a fortiori the critical voltages are always greater than the corona threshold.In Table 2we present the results for the convective instability in the non-ohmic liquid in the tip–plane and the triode configurations.As we see the magnitude I Æd 3isFig.8.The electric pressure pushes down the liquid,curvingthe liquidsurfaceFig.9.Convective instability (image from below).Tip–planeset-up.Liquid:silicone oil.V p =8.2kV,p =3.0cm,d =1.2mmFig.10.Coexisting instabilities (convective and rose window)in a non-ohmic liquid (silicone oil).Typical cells of the convective and of the rose-window instabilities are indicatedby black and white arrows ,respectively.It can be seen that the cell size of the convective instability is comparatively much smaller.A small rugose pattern appears in the image that is produced by the convective instability in the liquid surface.Triode set-up.V p =12kV,V g =3.0kV,I =1.0l A,d =1.2mm,p =3.0cm,h =1.5cmFig.11.Rose-window instability in an ohmic liquid (castor oil).The small wavelength instability is absent.V p =8.8kV,V g =2.0kV,I =0.63l A,d =1.2mm,p =3.0cm,h =1.5cmFig.12.The non-homogeneity of the electric field is greater in a tip–plane configuration.The first incipient instability appears at the centre of the electrode.Liquid:castor oil.V p =6.8kV,I =0.404l A,L =3.1cm,p =3.0cm,d =1.2mm731approximately constant.This can be explained if we con-sider that the liquid layer is in the space charge limited current (SCLC)regime:the voltage drop across an insulating liquid layer under strong charge injection is ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi8jd 3=9K l e l p.Then if I Æd 3~c ,c being a constant,it follows that V l is also a constant V l is proportional to T =e l V l /K l g ,which is the characteristic parameter of the instability criterion for an insulating liquid layer subjected to unipolar injection (where g is the dynamic viscosity).These results are quite similar to those in the work by Malraison and Atten (1991),where the experimental values are higher than the theoretical ones:Schneider and Watson (1970)predict I Æd 3=2.88Æ10)19Am 3for the critical current,while we obtained an average value I Æd 3~6.35Æ10)19Am 3,which corresponds to T c ~250.This difference could be due to a lower effective liquid layer thickness,as the liquid is pu-shed down by the corona wind (Fig.8).Nevertheless,an agreement of our experimental measurements with thetheory (Schneider and Watson 1970;Koulova-Nenova and Atten 1997)could not be expected as the experimental conditions in both set-ups are quite different to those in thetheory.(For example,the theory assumes that the liquid surface is equipotential which is not necessarily true in our experiments.)Besides,because of its small wavelength (less than 1mm),this instability is difficult to detect visually and the measured values could not be but an upper bound for the critical voltage.It is also interesting to note that in other experimental configurations the change of slope in the current vs.voltage curve is the best way to detect the instability,but this change of slope is not accessible in our experimental set-up because we cannot measure the voltage of the liquid surface (Lacroix et al.1975).2.2PhotographsBy use of a camera we can amplify the image of the liquid surface as seen from below.This is possible because of the transparency of the plane electrode and the liquids.Figure 9shows the convective instability in a tip–plane set-up,with a small characteristic wavelength.The liquid is silicone oil.Noticeable also is a firstdeformation with a much longer wavelength (5–10mm),which is the rose-window instability.This long wave instability has another important characteristic,which is a typical higher deformation amplitude and this makes it easier to be detected.In a non-ohmic liquid the rose window is a secondary instability because,in general,it appears once the convective instability has already developed.Since the convective instability is absent in liquids in the ohmic regime,its detection is also an experimental criterion for checking out the type of con-duction regime of a liquid.In Figs.10and 11the rose-window instability isshown for silicone and castor oil,respectively,in a triode set-up.Both instabilities coexist in the non-ohmic liquid whereas the convective instability is absent in the ohmic liquid.It should be mentioned that the rose-windowinstability does not develop abruptly but gradually.Afirst stationary deformation of high amplitude is detected at a given potential.This deformation appears at the centre of the electrode because the electric field there ismore intense owing to its non-homogeneity.This effect is stronger in a tip–plane configuration,where this inho-mogeneity is more important.Figure 12shows thatcloseFig.13.Rose window fully developed in an ohmic liquid(castor oil)in a triode set-up.The instability is stationary even at voltages higher than the critical value.V p =12kV,V g =3.25kV,I =1.55l A,p =3.0cm,h =1.5cm,d =1.2mm Fig.14.Rose-window instability in corn oil in a triode set-up.There is not a noticeable difference in the characteristic pattern for different ohmic liquids (compare with Fig.11).V p =9.0kV,V g =2.8kV,I =0.612l A,p =3.0cm,h =1.5cm,d =1.2mm Fig.15.Deformations at the centre of each grid square in thedecreasing region of the corona current in a triode set-up.Liquid:castor oil.V p =10kV,V g =5.0kV,I =0.713l A,p =3.0cm,h =1.5cm,d =1.2mm732to the instability threshold the deformation is only visible at the centre.If the electric potential is raised,theinstability begins to develop over all the electrode area.This transition is shown in Fig.11where the rose-win-dow instability is in an intermediate stage of develop-ment and in Fig.13where the instability has fully developed at a still higher electric potential (around 3kV).We have observed that the pattern of the rose-window instability is similar for different liquids.For instance,Fig.14corresponds to corn oil.For high grid voltages,when the electric current starts to decrease (see Fig.2),a rectangular pattern with cen-tred deformations at each rectangle becomes visible (see Fig.15).This additional pattern may be related to the concentration of the electric field lines in the centre of the grid squares and the corresponding electric pressure distribution onto the liquid surface.3Rose-window instability:discussionIn a former work (Vega and Pe´rez 2002),we have computed the linear instability criterion of the rose-window insta-bility in a perpendicular-field air/ohmic liquid interface.We used a standard treatment of the problem:a small perturbation is introduced in the electrohydrodynamic set of equations and the compatibility condition yields the characteristic eigenvalue in the dispersion relation.In this problem the eigenvalue is U =e 0V 2/<q >gh 3,indicating that the equilibrium between electric and gravitational pressure rules in the instability onset.The dispersion relation U (k ),where k is the non-dimensional wave number,is also a function of other magnitudes:U k ;Bo ;C ;S ;e ;d ÃðÞð1Þwhere all these magnitudes are non-dimensional:Bo ¼<q >gh 2c ;C ¼q 0h 2e 0V;S ¼r h 2K a e 0Vð2Þe ¼e l =e 0;d üd =hð3Þwhere <q >is the mass density jump at the interface,g the gravitational acceleration,h is the total length of the sys-tem h =L +d ,L and d being the air and the liquid layer thickness,respectively.The parameter Bo is the Bond number,which is a relation between the gravitational and capillary forces,C is the injection parameter that measures the strength of the injection and q 0is the space chargedensity at the injecting electrode.We refer to S as the apparent conductivity.It is a relation between the mag-nitudes of the non-ohmic and ohmic current densities in a non-ohmic layer with ion mobility K a and an ohmic layer with conductivity r .The apparent conductivity controls the interfacial instability mechanism in a non-ohmic/ohmic fluid interface.If the non-dimensional conductivity S is high enough the instability that first appears is normally the classical interfacial instability,which has an electric pressuredirected upwards.If this is the case,the critical voltages for a system with characteristic lengths of the order of 1cm for the air layer and 1mm for the liquid layer are of the order of 50–100kV.These critical values are of the order of those for the interfacial EHD instability in conducting liquids in the case of no injection.Conversely,if the non-dimensional conductivity S is low enough the instability that first appears is the rose-window instability,as the electric pressure is directed downwards,with critical val-ues around 1kV.The typical values of the magnitudes we deal with in our experiments (K a ~10)4m 2/(Vs),h ~10)2m,<q >~103kg/m 3)and the conductivity of the liquids we used are compatible with the occurrence of the rose-window instability.Concerning the injection level,Vega and Pe´rez (2002)found theoretically that the critical voltage for instability for low S is a strongly decreasing function of the parameter C in the weak injection region.Once the SCLC regime (strong injection)is reached the eigenvalue becomes independent of C .All this is concordant with our experi-mental observations.Below the corona onset there is no instability if no charge injection is applied.If a strong charge injection (a tip potential higher than the corona threshold)is applied,the critical values observed in the triode set-up are of the order of 1kV,as expected theo-retically.The critical points of Figs.3and 4show a weak dependence on the tip voltage (that controls the space charge in the triode system).This agrees with the fact that in the range of V g ~1kV and V p ~10kV the electric current increase with the tip voltage tends to be weak (see Fig.2).Figure 16compares the critical values of the electric potential obtained theoretically and experimentally (in ohmic regime).They agree in order of magnitude and show the same tendency.The theoretical values are cal-culated according to the linear model (Vega and Pe´rez 2002).They were obtained in the strong injection limit and neglecting the effects of capillary forces.The experimental critical values of the electric current I c (Figs.5and 6)areFig.16.Rose-window par-ison between theoretical and experimental critical voltages for the ohmic regime.The experimental series correspond to the triode set-up,with p )h =2.5cm,h =1.5cm.The critical grid voltage is plotted against the liquid layer thickness733。

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