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OH-radical induced degradation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 4-chloro-2-methyl

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OH-radicalinduceddegradationof2,4,5-trichlorophenoxyaceticacid(2,4,5-T)and4-chloro-2-methylphenoxyaceticacid(MCPA):Apulseradiolysisandgamma-radiolysisstudy

RobertZonaa,SonjaSolarb,n,KnudSehestedcaHBLVARosensteingasse,Rosensteingasse79,A-1170Vienna,Austria

bUniversityofVienna,FacultyofLifeSciences,DepartmentofNutritionalSciences,SectionRadiationBiology,Althanstrasse14,A-1090Vienna,Austria

cRisoeNationalLaboratories,DK-4000Roskilde,Denmark

articleinfoArticlehistory:Received21September2011Accepted21September2011Availableonline29September2011Keywords:2,4,5-Trichlorophenoxyaceticacid(2,4,5-T)4-Chloro-2-methylphenoxyaceticacid(MCPA)OH-radicalsPulseradiolysisGamma-radiolysisDegradationproductsabstractThereactionsofdOH,HdandeaqÀwith2,4,5-trichlorophenoxyaceticacid(2,4,5-T)and4-chloro-2-methylphenoxyaceticacid(MCPA)werestudiedbypulseradiolysis.ThesiteofdOH-radicalsadditiontothearomaticringof2,4,5-Twasfoundtobe—C1:$18%,C2/C4/C5:total$28%andC3/C6:total$41%.TheoverallrateconstantswithOH-radicalswerek(dOHþ2,4,5-T)¼6.4(70.5)Â109moldmÀ3sÀ1andk(dOHþMCPA)¼8.5(70.8)Â109moldmÀ3sÀ1.Theradiationinduceddecompositionofthepesti-cides,chloride-andproductformation(phenoliccompounds,aliphaticacids)wasstudiedbygammaradiolysisasafunctionofdose.Amechanismforacetateformationisdiscussed.Thepresenceofoxygenduringirradiationaffectedthedecompositionrateonlyindiscernibly,however,chlorideelimination,ringfragmentation(formationofaliphaticacids),TOC-andtoxicityreductionwerestronglyenhanced.Forcompleteremovalof500mmoldmÀ3herbicidesadoseof$4kGywasrequired.Usingairsaturationduringirradiationareductionof37–40%oftheTOCwasobservableat5kGy,detoxification(luminescenceinhibitiono20%)wasachievedwith10kGy.&2011ElsevierLtd.Allrightsreserved.

1.IntroductionInthelastdecadesphenoxyaceticacidderivativeshavebeenoneofthemostcommonlyappliedherbicidesinagriculture,andconsequently,theycanbepresenttogetherwiththeirdegrada-tionproductsinnaturalwaterresources.Contaminationofwatersandsoilcanalsooccurfrompesticidedischargesfrommanufac-turingplants,fromstoragesitesandrunoffsfromvegetationandsoil.Forremediationofwatersandwasteadvancedoxidationprocesses(AOPs)e.g.ionizingradiation(Zonaetal.,2002a;Drzewiczetal.,2004;PellerandKamat,2005;Bojanowska-Czajkaetal.,2006),UV-radiation/ozone/photocatalysis(M¨ulleretal.,1998;Benitezetal.,2004;Zertaletal.,2004)sonolysis(Pelleretal.,2001;Uenoetal.,2009),electrochemicaldegrada-tion(Brillasetal.,2003a,2003b)aswellasbiodegradation(KuhlmannandKaczmarzcyk,1995;Celisetal.,2008)havebeensuggested.AllAOPsarebasedonin-situoxidationbydOHradicals

(e.g.Pelleretal.,2004).Manymicroorganismscausingbiodegra-dationhavebeenisolated(e.g.Kitagawaetal.,2002).Inthismetabolicpathwayhydroxylationhasbeenfoundtobean

essentialstep.For2,4-Dthefollowingsequenceofdegradationproductswasreported:2,4-dichlorophenol,3,5-dichlorocatechol,2,4-dichloromuconate,2-chlorodienelactoneand2-chloromaley-latcetate.MCPAfollowsananalogousroute(SmithandBeadle,2008).InthepresentstudywaterandionizingradiationwereusedasdOHradicalsource.

TheobjectiveofthisreportwastoelucidatethemechanisticdetailsofdOH-radicalattachmentonthearomaticringof2,4,5-TandMCPA,andtoanalyzetheconsequentlyformedproducts.Further,theeffectofoxygenduringirradiationonthedegrada-tion-andchlorideeliminationrate,onthealiphaticacidforma-tion,aswellasonthemineralizationprocesswasassessed.Inaddition,thewaterqualityafterirradiationwasdeterminedbytoxicitymeasurements.

2.Experimental2.1.Chemicals,solutionsandabbreviations2,4,5-Trichlorophenoxyaceticacid(2,4,5-T),4-chloro-2-methylphenoxyaceticacid(MCPA),2,4,5-trichlorophenol(2,4,5-TCP),4-chloro-2-methylphenol(4-CMP),2,4-dichlorophenoxya-ceticacid(2,4-D)andallchemicalsusedwereofhighestpurity

ContentslistsavailableatSciVerseScienceDirectjournalhomepage:www.elsevier.com/locate/radphyschemRadiationPhysicsandChemistry

0969-806X/$-seefrontmatter&2011ElsevierLtd.Allrightsreserved.doi:10.1016/j.radphyschem.2011.09.012

nCorrespondingauthor.Tel.:þ431427754970;fax:þ431427754964.

E-mailaddress:sonja.solar@univie.ac.at(S.Solar).

RadiationPhysicsandChemistry81(2012)152–159gradeavailable(Aldrich,Merck).ForsamplepreparationwaterwasdistilledandfurtherpurifiedusingDirect-Q3UVpurificationsystem(Millipore,Bedford,MA,USA).Thesolutions(500mmoldmÀ3i.e.100ppmMCPAand128ppm2,4,5-T)werepurgedwithN2O(Stickoxydul,p.n.;MesserAustria,Vienna,

Austria)forabout30min,oruseddirectly(aeratedsolution,A),saturatedwithair(AS)and/orsaturatedwithoxygen(OS)duringirradiation.ThepH($9)wasadjustedwithNaOH.

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高效液相色谱荧光检测法测定药物中的氯乙酰氯

高效液相色谱荧光检测法测定药物中的氯乙酰氯

化学分析计量CHEMICAL ANALYSIS AND METERAGE第30卷，第1期2021年1月V ol. 30，No. 1Jan. 202159doi ：10.3969／j.issn.1008–6145.2021.01.012高效液相色谱荧光检测法测定药物中的氯乙酰氯汤加园，陈向明(滨州医学院药学院，山东烟台　264003)摘要　建立测定药物中氯乙酰氯含量的高效液相色谱–荧光检测方法。

以吖啶酮乙酰肼为荧光标记试剂，对氯乙酰氯进行柱前衍生。

在室温下反应15 min ，衍生产率达到最大。

衍生溶液在XDB–C 18柱上，以水和乙腈为流动相进行分析，激发波长和发射波长分别为255 nm 和429 nm 。

氯乙酰氯浓度在1～1 000 nmol ／L 范围内与色谱峰面积具有良好的线性关系，线性相关系数r =0.999 9。

方法的检出限为0.35 nmol ／L ，仪器精密度和方法精密度分别为0.52%和0.67%(n =6)。

样品加标回收率为92.5%～95.6%。

该方法简单、准确，精密度良好，可用于测定药物中氯乙酰氯的残留量。

关键词　高效液相色谱；荧光检测；氯乙酰氯中图分类号：O657.7 文献标识码：A 文章编号：1008–6145(2021)01–0059–04Determination of chloroacetyl chloride in drug substance by high performanceliquid chromatography with fluorescence detectionTang Jiayuan ， Chen Xiangming(School of Pharmacy ， Binzhou Medical University ， Yantai 264003， China)Abstract A high performance liquid chromatography method coupled with fluorescence detection to determine chloroacetyl chloride in drug substance was developed. Acridone acetyl hydrazine was used as fluorescence labeling reagent and chloroacetyl chloride was derived before column. Optimum derivatization was obtained at room temperature for 15 min. The derivative was separated on a reversed-phase XDB–C 18 column in conjunction with water and acetonitrile as mobile phase. The excitation and emission wavelengths were 255 nm and 429 nm respectively. The concerntration of chloroacetyl chloride had good linear ralationship with the chromatographic peak area in the range of 1–1 000 nmol ／L, the linear correlation coefficient r =0.999 9. The instrument precision and method precision were 0.52%, 0.67%(n =6)，respectively. The detection limit of the method was 0.35 nmol ／L ，and the recoveries were in the range of 92.5%–95.6%. The method is simple ，accurate and showed good repeatability ，which can be used to determine the content of chloroacetyl chloride in drug substance.Keywords high performance liquid chromatography; fluorescence detection; chloroacetyl chloride药物中的遗传毒性杂质是一类能损伤细胞遗传物质并引起基因突变或体内诱变的物质，较少的摄入量就能够对身体健康产生严重的损害［1–2］。

高效液相色谱法快速测定土壤中的2,4-D残留

高效液相色谱法快速测定土壤中的2,4-D残留

高效液相色谱法快速测定土壤中的2,4-D残留陈军【摘要】本方法采用高效液相色谱法对农用地土壤中的2,4-D进行批量快速检测.通过超声震荡提取,离心过0.22um有机相膜上机,在紫外230nm处测定其吸光强度,外标法定量.方法检出限为:0.90ug/kg;回收率:88.7%-98.8%;精密度:2.36%-3.67%.结果表明该方法能够满足农用地土壤样品中2,4-D残留mg.kg-1痕量级测量.【期刊名称】《化工中间体》【年(卷),期】2017(000)002【总页数】2页(P41-42)【关键词】高效液相色谱法;2,4-D残留;超声震荡提取【作者】陈军【作者单位】深圳市华保科技有限公司广东 518057【正文语种】中文【中图分类】T2，4-D概述：2，4－二氯苯氧乙酸2，4－dichlorophenoxyacetic acid。

具有代表性的合成植物生长激素（auxin），简称2，4－D。

自齐默尔曼（P.W.Zimmermann，1942）等发现了2，4-D的作用以来，以此物质为中心的许多合成植物生长素应用于农业有了迅速的发展，此物质被大规模地利用为除草剂及防止果实早期脱落剂等。

撒入土中的2，4－D可为革兰氏阴性球菌和水生黄杆菌（Flavobacteriumaquatile）等细菌所分解。

但是由于2,4-D在土壤中的吸附作用导致除草剂土壤吸附残留，危害后茬。

据卫生部网站消息，2，4-二氯苯氧乙酸等38种食品添加剂已不具备技术必要性，卫生部拟根据有关规定予以撤销。

本方法探讨了使用HPLC方法快速批量测定农用地土壤中的2，4-D残留，通过超声震荡提取，离心过膜净化，具有操作方便快捷，可批量处理，回收率好，选择性强的优点，液相分析采用甲醇+水（调PH3.0-5.0）流动相等度洗脱，分离效果好，灵敏度高，干扰少，回收率精密度能满足检测要求，实用性强。

(1)材料与试剂甲醇、丙酮：色谱纯；磷酸：分析纯；超纯水；0.22um水相膜和有机相膜；2，4-D标准物质纯度99.8%。

CuOBi_(2)O_(3)光催化耦合过一硫酸盐氧化降解盐酸四环素

CuOBi_(2)O_(3)光催化耦合过一硫酸盐氧化降解盐酸四环素

'£朽知库环境工程学报第15卷第3期2021年3月Vol. 15, No.3 Mar. 2021Eco-Environmental Knowledge Web C hinese Journal of Environmental Engineering@(010) 62941074文章栏目：水污染防治DOI 10.12030/j.cjee.202008112 中图分类号X701.3 文献标识码A丁丽丹，周家斌，刘文博，等.Cu0/Bi203光催化耦合过一硫酸盐氧化降解盐酸四环素[J].环境工程学报，2021. 15(3): 898- 910.DING Lidan, ZHOU Jiabin, LIU Wenbo, et al. Oxidative degradation of tetracycline hydrochloride by Cu0/Bi203 photocatalysis coupling with peroxymonosulfate[J]. Chinese Journal of Environmental Engineering, 2021, 15(3): 898-910.C u0/B i203光催化耦合过一硫酸盐氧化降解盐酸 四环素丁丽丹、周家斌刘文博\陈新2,冯芹芹2,杨玉玲\张天磊11. 西南石油大学化学化工学院，成都6105002. 武汉理工大学资源与环境工程学院，武汉430070第一作者：丁丽丹（1995—)，女，硕士研究生。

研究方向：水处理高级氧化技术。

E-mail: ***************** *通信作者：周家斌（1972—），男，博士，教授。

研究方向：环境功能材料与污染控制：E-mail: ****************摘要利用共沉淀-浸渍法合成了基于可见光响应的Cu0/Bi203复合催化剂，并对其光催化活化过一硫酸盐 (PM S)去抗生素盐酸四环素（TC-HC1)的性能进行了探究。

基于基因毒性和对单抗聚集影响的聚山梨酯中醛限度的控制

基于基因毒性和对单抗聚集影响的聚山梨酯中醛限度的控制

学报Journal of China Pharmaceutical University2022，53（1）：67-7367基于基因毒性和对单抗聚集影响的聚山梨酯中醛限度的控制王珏1#，江颖2#，肖新月1，杨锐1，孙会敏1*，涂家生3**（1中国食品药品检定研究院，国家药品监督管理局药用辅料质量研究与评价重点实验室，北京100050；2上海市医疗器械化妆品审评核查中心，上海200020）；3中国药科大学，国家药品监督管理局药物制剂及辅料研究与评价重点实验室，南京210009；摘要通过建立HPLC柱前衍生化法对不同厂家的聚山梨酯80和聚山梨酯20中甲醛、乙醛进行检测分析，并在不同条件下监测甲醛和乙醛对阿达木单抗聚集的影响，分别从基因毒性杂质控制和对单抗制剂稳定性影响两方面综合考量，初步得出二者的控制限度。

HPLC柱前衍生化法采用2，4-二硝基苯肼（2，4-DNPH）作为衍生化试剂，以乙腈和水为流动相，在C8（4.6mm×150mm，5μm）色谱柱上梯度洗脱进行分离，检测波长为360nm，用外标法定量。

方法学验证结果表明，该方法适用于聚山梨酯80和聚山梨酯20中微量甲醛和乙醛的定量分析。

对不同厂家不同批次的聚山梨酯80和聚山梨酯20中甲醛或乙醛的检测分析表明二者含量差异较大，聚山梨酯80中甲醛和乙醛含量明显高于聚山梨酯20；用分子排阻色谱法对经甲醛和乙醛处理的阿达木单抗分子聚集体变化进行监测后发现，甲醛对阿达木聚集的影响显著高于乙醛。

按照《人用药品注册技术国际协调会议指南：诱变性杂质评估和控制》（ICH M7）的要求从风险评估的角度计算单抗制剂用聚山梨酯80和聚山梨酯20中甲醛和乙醛的杂质限度，结合对单抗聚集稳定性的影响，给出其中甲醛和乙醛初步的限度建议为：分别不得过7μg/g和765μg/g。

关键词基因毒性；聚山梨酯80；聚山梨酯20；甲醛；乙醛；限度控制；单抗；聚集中图分类号R917文献标志码A文章编号1000-5048（2022）01-0067-07doi：10.11665/j.issn.1000-5048.20220110引用本文王珏，江颖，肖新月，等.基于基因毒性和对单抗聚集影响的聚山梨酯中醛限度的控制［J］.中国药科大学学报，2022，53（1）：67–73.Cite this article as：WANG Jue，JIANG Ying，XIAO Xinyue，et al.Control strategy for the limit of aldehydes in polysorbates based on geno⁃toxicity and influence on the aggregation of monoclonal antibody［J］.J China Pharm Univ，2022，53（1）：67–73.Control strategy for the limit of aldehydes in polysorbates based on geno⁃toxicity and influence on the aggregation of monoclonal antibody WANG Jue1#,JIANG Ying2#,XIAO Xinyue1,YANG Rui1,SUN Huimin1*,TU Jiasheng3**1NMPA Key Laboratory for Quality Research and Evaluation of Pharmaceutical Excipients,National Institutes for Food and Drug Control,Beijing100050;2Shanghai Municipal Evaluation and Verification Center for Medical Devices and Cosmetics,Shanghai 200020;3NMPA Key Laboratory for Research and Evaluation of Pharmaceutical Preparations and Excipients,China Pharmaceutical University,Nanjing210009,ChinaAbstract An HPLC pre-column derivatization detection method was established to detect and analyze the form⁃aldehyde and acetaldehyde in polysorbate80and polysorbate20from different manufacturers.The effects of aldehyde and acetaldehyde on the aggregation of adalimumab under different conditions were monitored.Based on the control of genotoxic impurities and the influence on the stability of monoclonal antibody preparations,the control limits of the two chemicals were preliminarily obtained.2,4-dinitrophenylhydrazine(2,4-DNPH)was收稿日期2021-08-10通信作者*Tel：************E-mail：sunhm@**Tel：************E-mail：jiashengtu@基金项目中国食品药品检定研究院中青年发展研究基金资助项目（No.2018C7）#王珏与江颖为共同第一作者学报Journal of China Pharmaceutical University 2022，53（1）：67-73第53卷applied as the derivatization reagent in HPLC pre -column derivatization;acetonitrile and water were used asmobile phase to perform a gradient elution on a C 8(4.6mm ×150mm,5μm)chromatographic column.The detection wavelength was 360nm,and the external standard method was used for quantification.Verification results showed that the method was suitable for the quantitative analysis of trace formaldehyde and acetaldehyde in polysorbate 80and polysorbate 20.The detection and analysis of formaldehyde or acetaldehyde in different batches of polysorbate 80and polysorbate 20from different manufacturers showed that the content of formalde⁃hyde and acetaldehyde were quite different.The content of formaldehyde and acetaldehyde in polysorbate 80were significantly higher than those of polysorbate 20.After monitoring the changes of adalimumab aggregates treated by formaldehyde and acetaldehyde by size exclusion chromatography (SEC),it was found that the effect of formaldehyde on adalimumab aggregation was significantly higher than that of acetaldehyde.According to the requirements of ICH M7(International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use,M7:Assessment and Control of DNA Reactive (Mutagenic)Impurities in Pharmaceuticals to Limit Potential Carcinogenic Risk),the impurity limits of formaldehyde and acetaldehyde in polysorbate 80and polysorbate 20for monoclonal antibody preparations were calculated from the perspective of risk bined with the influence on the aggregation stability of monoclonal antibodies,the prelimi⁃nary limis for acetaldehyde and acetaldehyde were recommended to be ≤7μg/g and ≤765μg/g,respectively.Key words genotoxicity;polysorbate 80;polysorbate 20;formaldehyde;acetaldehyde;limit control;monoclo⁃nal antibody;aggregationThis study was supported by the Youth Development Foundation of National Institutes for Food and Drug Control (No.2018C7)#WANG Jue and JIANG Ying contributed equally to this work在药用辅料中，甲醛和乙醛通常是经降解产生的小分子杂质，尤其在聚氧乙烯类或包含聚氧乙烯链段的药用辅料（如聚山梨酯20、聚山梨酯80等）中可能存在，其降解途径如图1所示［1］。