首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 140 毫秒
1.
基体辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)法因其具有测定质量范围大、灵敏度高、速度快及精确度好等优点,近年来已成为测定多肽、蛋白质、核酸、多糖等生物大分子分子量及其一级结构的有力工具。此外,MALDI-TOF-MS法还可用于C60、聚合物等非生命物质的测定分析^[1,2]。目前,MALDI-TOF-MS法已广泛应用于蛋白质及多肽的分子量和有序列的测定,但将该法用于DNA测定尚未达到与蛋白质相当的水平,但近期的研究已取得了较大进展[3-5]。DNA中A,G,C,T等4种碱基质量相差不大,因此,获取高分辨率的质谱图是保证MALDI-TOF-MS法测序结果准确无误的重要前提。本文报道了用MALDI-TOF-MS法测定了4种DNA样品d(C)10,d(G)10,d(T)18和d(TTACTCTGTTAATGTCTTTG)的高分辨质谱分析结果。  相似文献   

2.
表面活性剂存在下雌激素的直接电化学分析   总被引:5,自引:0,他引:5  
雌二醇(E2)、雌三醇(E3)和雌酮(E1)是人体内3种重要的雌激素,它们在妇女的生殖生育方面发挥重要的作用。人体雌激素缺乏或过乘会导致诸多疾病。雌激素的检测方法已有不少报道,如气相色谱-质谱(GC-MS)、液相色谱(LC)以及化学发光免疫法等。E2,E1和E3的结构相似,且均具有疏水性及非电活性,用电化学直接测定十分困难,一般只能间接测定。本文报道了一种新的电化学分析方法。该方法对三种雌激素有十分灵敏的伏安响应,可用于微量测定。  相似文献   

3.
卡尔曼滤波伏安法同时测定炼油废水中苯酚和苯胺的研究   总被引:4,自引:0,他引:4  
炼油废水中主要含有石油类、苯酚和苯胺等物质。由于石油类、苯酚和苯胺等毒性极大,排放含这些物质的废水将对环境造成极大的污染,严重影响社会的可持续发展,故需测定炼油废水中这些物质的含量以便于处理控制。目前常用的测定石油类和苯酚的方法有石油醚萃取紫外分光光度法,CC14萃取红外光谱法和蒸馏4-AAP比色法。这些方法的主要缺点是水样预处理步骤繁琐,工作效率低,测定成本高,并且因使用有机溶剂而造成二次污染,危害测试人员的健康。此外,对于苯酚和苯胺含量较低的水样,由于萃取和蒸馏效率的制约,难以准确测量。我们用自制的蒙脱石-石墨-聚氯乙烯复合电极和卡尔曼滤波伏安法对模拟炼油废水中苯酚和苯胺进行了同时测定,取得了满意的效果,该法简单、准确、快速,具有较大的推广应用价值。  相似文献   

4.
在研究了苯酚(Ph-OH)和十二烷基苯磺酸钠(SDBS)荧光性质的基础上,以P-矩阵计算混合体系中苯酚和十二烷基苯磺酸钠.方法灵敏度高,选择性好,简便快速,应用于环境水样测定结果令人满意.  相似文献   

5.
1引言铬(Ⅵ)、苯酚和4-硝基酚是我国环境优先监测的工业污染物,其测定方法一直是环境分析中研究的重要课题。十二烷基苯磺酸钠(SDBS)是我国使用量最大的洗涤剂,它对环境造成的污染不容忽视。这4种物质有许多检测方法,但大多是用不同方法分别测定。本文建立了以甲醇、乙醚和HAc-NaAc缓冲溶液为流动相,反相高效液相色谱法分离和测定铬(Ⅵ)、苯酚、4-硝基酚和SDBS4种污染物的分析方法,并应用于环境水样中。2实验部分2.1仪器与试剂SSI222D型高效液相色谱仪,UV-500型紫外-可见检测器,Ch…  相似文献   

6.
表面活性剂的基体辅助激光解吸电离/质谱分析表征   总被引:1,自引:0,他引:1  
利用基体辅助激光解吸电离/质谱(MALDI-MS)技术对表面活性剂的分析表征进行了详细研究。以2,5-二羟基苯甲酸作为基体,考察MALDI样品制备方法如液滴干燥法、快速干燥法及三明治法对测定结果的影响,发现三明治方法更适合表面活性剂的分析。MALDI可以准确测定离子型表面活性剂的分子量,同时对于非离子型表面活性剂,还可以测定其平均聚合度和分子量的分布。  相似文献   

7.
某些天然和人工合成有机化学物质能够干扰人类和野生动物内分泌系统的正常功能(一般称为“内分泌干扰物质”, EDCs), 从而对人类和野生动物种群的生存和持续繁衍造成严重威胁. 鉴于人工合成化学品种类繁多、结构复杂, 发展基于结构的快速筛选方法, 对环境中污染物进行筛选和评价, 具有重要的实际意义. 应用一种新的分子结构表征方法——分子全息, 利用多变量统计方法——偏最小二乘分析(PLS), 以105种典型的环境雌激素类化合物为研究对象, 发展了完全基于分子结构的定量预测模型, 可以对环境中有机污染物的雌激素活性进行比较准确的预测和快速筛选.  相似文献   

8.
用分光光度滴定法在25.0℃时测定了不同pH值下α-,β-,γ-环糊精以及1mol/L NaOH水溶液中α-和β-环糊精双核铜配合物与4-取代苯酚形成超分子配合物的稳定常数。化学计量法表明,主体环糊精及环糊精双核铜配合物与客体4-取代苯酚形成了1:1的超分子配合物。从主-客体间的尺寸关系、pH值、多点识别和诱导契合作用等因素讨论了环糊精及环糊精双核铜配合物对客体4-取代苯酚的分子识别机制。结果表明  相似文献   

9.
苯酚是重要的有机合成中间体,当前主要通过异丙苯法合成苯酚的技术路线存在制备流程长、消耗丙烯、副产丙酮等不足。以分子氧为氧化剂由苯氧化直接合成苯酚则具有潜在重大的经济效益、社会效益和环境效益,已成为催化与有机合成等研究领域中极具挑战性的热点课题之一。本文较为系统地总结了分子氧氧化苯通过一步法合成苯酚的研究工作,着重综述了用于该反应的催化剂如Pd、Cu、V等金属或其化合物,也归纳了影响此反应的主要因素,并介绍相应的反应机理。最后,对分子氧催化氧化苯合成苯酚反应的研究提供了一些建议和展望。  相似文献   

10.
1引言 超分子化学的迅猛发展引起了化学界广泛的重视。本文用X射线粉末衍射仪以苯酚与三醋酸纤维素为例研究了他们之间的超分子作用及它们间的作用机理和结构。苯酚的羟基与三醋酸纤维素酯羰基之间通过氢键以及二醋酸纤维素的特有空隙系统,形成一种包合络合物。2实验部分2.1仪器及试剂Rigaku D/max-3c X射线粉末衍射仪(理学公司);苯酚(A.R.);微晶纤维素(层析用);羧甲基纤维素(CMC)(山东鱼台助剂厂);三醋酸纤维索(合成)。2.2实验方法取固定量的苯酚分别加入一定量的二醋酸纤维素、微晶纤维…  相似文献   

11.
A sensitive and simple method based on ultrasonication extraction with a hexane/acetone (2:1, v/v) mixture, followed by clean up of the extract by solid-phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) detection, has been developed and validated for the analysis of 20 estrogenic endocrine-disrupting chemicals (EEDCs) including phenolic xenoestrogens, synthetic and natural estrogens in river sediment. After extraction and purification, analytes are derivatised with a BSTFA/TMCS/pyridine (49:1:50, v/v/v) mixture and quantified by GC/MS. The GC/MS method involves switching between electron ionisation (EI) and chemical ionisation (CI); it also switches between selected ion storage and tandem mass spectrometry detection. The applicability of the method has been demonstrated by analysing extracts of French river sediments for which bioanalytical tests (in vitro) had already shown that they were impacted by estrogenic endocrine disrupters. The biological contribution of all the products detected in each sediment extract was compared to the estrogenic activity measured by bioassays.  相似文献   

12.
Environmental analytical chemistry has recently changed focus from analysis of non-polar, persistent contaminants (e.g. polychlorinated biphenyls and dioxins) to more polar and labile compounds that interfere with biological processes. For example, natural and synthetic estrogens and their metabolites have been detected in sewage treatment plant effluents at nanogram/liter concentrations that are similar to those at which both total sex reversal and intersex (containing both testes and ova) is induced in fish exposed to these compounds in laboratory experiments. The development of techniques for the analysis of natural and synthetic estrogens in biological fluids (i.e. serum and urine) has been a priority in the biomedical field. However, the recent recognition that estrogen hormones are contaminants in the environment that may contribute to endocrine disruption has focused attention on the need for highly sensitive and specific techniques that are applicable for trace analysis in complex environmental matrices. Three optimized mass spectrometric protocols have been developed for the determination and quantitation of steroid hormones in environmental matrices using gas chromatography/tandem mass spectrometry (GC/MS/MS), liquid chromatography/mass spectrometry selected ion monitoring, (LC/MS - SIM) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The advantages and disadvantages of each method are presented.  相似文献   

13.
建立了一种快速、灵敏、准确的同时测定牛蛙全血中双酚A、己烯雌酚、己二烯雌酚、己烷雌酚、4-叔辛基酚和4-壬基酚等6种酚类环境雌激素的分散固相萃取-超快速液相色谱-串联质谱(dSPE-UFLC-MS/MS)分析方法。牛蛙全血样品经含0.1%(v/v)甲酸的甲醇溶液沉淀蛋白后,利用自制的氨基功能化Fe3O4磁性高分子复合微粒(EDA-MPs)作为dSPE吸附剂进行净化,着重考察了沉淀剂、吸附净化时间、吸附剂用量等因素对6种酚类环境雌激素回收率的影响。采用Shim-pack XR-ODSII(100 mm×2.0 mm, 2.2 μm)反相液相色谱柱进行分离,在电喷雾离子源(ESI)负离子多反应监测(MRM)模式下进行检测。结果表明: 6种酚类环境雌激素在0.5~100.0 μg/L范围内具有良好的线性关系(r2≥0.9996),方法的定量限(信噪比大于10)为0.075~0.40 μg/L,方法的精密度为0.6%~6.3%,空白样品中3个不同水平的添加回收率为95.0%~110.0%。本方法适用于牛蛙全血中6种酚类环境雌激素的同时测定。  相似文献   

14.
This review highlights the analytical chemistry, environmental occurrence, and environmental fate of individual stereoisomers of chiral emerging pollutants, which are modern current-use chemicals of growing environmental concern due to their presence in the environment and potential for deleterious effects. Comparatively little is known about individual stereoisomers of pollutants, which can have differential toxicological effects and can be tracers of biochemical weathering in the environment. Stereoisomers are resolved by gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrophoresis (CE). Separation techniques in environmental analysis are typically coupled to mass spectrometry (MS) and tandem mass spectrometry (MS/MS), as these provide the sensitivity and selectivity needed. The enantiomer composition of phenoxyalkanoic and acetamide herbicides, organophosphorus and pyrethroid pesticides, chiral polychlorinated biphenyl metabolites, synthetic musks, hexabromocyclododecane, and pharmaceuticals in the environment show species-dependent enantioselectivity from biotransformation and other biologically mediated processes affecting enantiomers differentially. These enantiomer compositions are useful in detecting biologically mediated environmental reactions, apportioning sources of pollutants, and gaining insight into the biochemical fate of chiral pollutants in the environment, which are needed for accurate risk assessment of such chemicals.  相似文献   

15.
In the present work, a review of the analytical methods developed in the last 15 years for the determination of endocrine disrupting chemicals (EDCs) in human samples related with children, including placenta, cord blood, amniotic fluid, maternal blood, maternal urine and breast milk, is proposed. Children are highly vulnerable to toxic chemicals in the environment. Among these environmental contaminants to which children are at risk of exposure are EDCs —substances able to alter the normal hormone function of wildlife and humans—. The work focuses mainly on sample preparation and instrumental techniques used for the detection and quantification of the analytes. The sample preparation techniques include, not only liquid–liquid extraction (LLE) and solid-phase extraction (SPE), but also modern microextraction techniques such as extraction with molecular imprinted polymers (MIPs), stir-bar sorptive extraction (SBSE), hollow-fiber liquid-phase microextraction (HF-LPME), dispersive liquid–liquid microextraction (DLLME), matrix solid phase dispersion (MSPD) or ultrasound-assisted extraction (UAE), which are becoming alternatives in the analysis of human samples. Most studies focus on minimizing the number of steps and using the lowest solvent amounts in the sample treatment. The usual instrumental techniques employed include liquid chromatography (LC), gas chromatography (GC) mainly coupled to tandem mass spectrometry. Multiresidue methods are being developed for the determination of several families of EDCs with one extraction step and limited sample preparation.  相似文献   

16.
Novel approaches to the analysis of steroid estrogens in river sediments   总被引:1,自引:0,他引:1  
A wide range of estrogenic contaminants has been detected in the aquatic environment. Among these, natural and synthetic steroid estrogens, typically present in municipal sewage-treatment plant (STP) effluents, are the most potent. In this study a new GC–MS method has been developed for direct analysis of five major steroid estrogens (estrone, 17β-estradiol, 17α-ethinylestradiol, dienestrol, and diethylstilbestrol) in river sediments. Four GC–MS systems used for analysis of underivatized analytes in purified extracts were compared. Relatively low detection limits (1.5–5 ng g−1 dried sediment) and good repeatability of GC splitless injection (RSD 1–2%) were achieved by use of a system combining low-pressure gas chromatography with a single-quadrupole mass analyzer (LP-GC–MS). Use of orthogonal gas chromatography (GC×GC) hyphenated with high-speed time-of-flight mass spectrometry (HSTOF-MS) enabled not only significantly better resolution of target analytes, and their unequivocal identification, but also further improvement (decrease) of their detection limits. In addition to these outcomes, use of this unique GC×GC–TOF-MS system enabled identification of several other non-target chemicals, including pharmaceutical steroids, present in purified sediment extracts.  相似文献   

17.
A simple and sensitive analytical methodology is developed for rapid screening and quantification of selected estrogenic endocrine disrupting chemicals and bisphenol A from intact milk using fabric phase sorptive extraction in combination with high‐performance liquid chromatography coupled to ultraviolet detection/tandem mass spectrometry. The new approach eliminates protein precipitation and defatting step from the sample preparation workflow. In addition, the error prone and time‐consuming solvent evaporation and sample reconstitution step used as the sample post‐treatment has been eliminated. Parameters with most significant impact on the extraction efficiency of fabric phase sorptive extraction including sorbent chemistry, sample volume, extraction time have been thoroughly studied and optimized. Separation of the selected estrogenic endocrine disrupting chemicals including α‐estradiol, hexestrol, estrone, 17α‐ethinyl estradiol, diethylstilboestrol, and bisphenol A were achieved using a Zorbax Extend‐C18 high‐performance liquid chromatography column (15 cm × 4.6 mm, 5 μm particle size). The limit of detection values obtained in fabric phase sorptive extraction with high‐performance liquid chromatography with ultraviolet detection ranged from 25.0 to 50.0 ng/mL. The method repeatability values were 3.6–13.9 (relative standard deviation, %) and intermediate precision values were 4.6–12.7 (relative standard deviation, %). The fabric phase sorptive extraction method was also coupled to liquid chromatography with tandem mass spectrometry for identifying each endocrine disrupting chemical at 10 ng/mL.  相似文献   

18.
Environmental endocrine disrupting chemicals(EDCs) or environmental estrogens pose severe healthhazard to wildlife and humans. They are believed to bethe main cause of the weakening activity and secretionof sex hormone, sperm declination, abnormal repro-d…  相似文献   

19.
Fish can be exposed to a complex mixture of chemical contaminants arising from the exposure to wastewater treatment works (WwTWs) effluents. Some of these contaminants are estrogenic and have been associated with feminisation of male fish and the presence of populations containing intersex individuals. However the detection of trace levels (ng/L) of estrogenic chemicals surface waters can be difficult and does not give information on the exposure of aquatic organisms to these contaminants. In this study we assessed whether the analysis of estrogenic substances that bioconcentrate in fish bile can be used to detect the exposure of fish to feminising contaminants in receiving waters and effluents, and thus facilitate their monitoring of these substances in aquatic environments. Estrogenic metabolites in bile were deconjugated using enzymatic hydrolysis and partially purified by solid phase extraction. Steroidal and xenoestrogens were derivatized to their trimethylsilyl ethers and quantified by gas–liquid chromatography–mass spectrometry (GC–MS/MS) using multiple reaction monitoring. The method was validated using spiked bile samples from immature female rainbow trout (Oncorhynchus mykiss) as well as bile from sexually mature roach (Rutilus rutilus) that had been exposed to either tap water or an undiluted estrogenic effluent for 10 days or captured from a river site downstream of a WwTWs effluent discharge. The mean recovery of target analytes from spiked bile was between 86 and 99% and the limit of detection was between 0.1 and 0.7 ng/mL bile for bisphenol A (BPA), 17β-estradiol (E2), estrone (E1) and 17α-ethinylestradiol (EE2), and 11, 60 and 327 ng/mL bile for branched nonyl chain isomeric mixtures of 4-nonylphenolethoxylate (NP1EO), 4-nonylphenol (NP) and 4-nonylphenoldiethoxylate (NP2EO), respectively. All target analytes were detected in bile from roach exposed directly to a WwTWs effluent, with concentrations between 6–13 μg/mL bile for NP, 18–21 μg/mL for NP1EO, 75–135 μg/mL for NP2EO, 0.7–2.5 μg/mL for BPA, E2 and E1 and 17–29 ng/mL for EE2. With the exception of NP2EO, all analytes were detected in at least 2 out of the 5 fish sampled from the River Thames. BPA and NP1EO were detected in all three reference fish held in tap water indicating possible contamination from laboratory plastics. The work shows that analysis of 20–100 μL quantities of bile could be a useful approach in detecting exposure to mixtures of estrogenic contaminants taken up by fish from WwTW effluents and has the potential for monitoring the efficacy of remediation strategies that may be adopted for reduction of these endocrine disrupting chemicals in the aquatic environment.  相似文献   

20.
环境内分泌干扰物(EDCs)是指干扰生物体内保持自身平衡和调节发育过程中天然激素的合成、分泌、运输、代谢、结合、反应、消除等生物过程的外源性化学物质,这类物质的存在会干扰人类和野生动物的内分泌系统,带来生殖障碍、发育异常、免疫功能减弱等问题。EDCs,尤其是使用最为广泛的酚类EDCs,在水环境中的污染特征研究已是当前科学界和公众共同关注的热点问题之一。环境样品基质非常复杂,使得痕量酚类EDCs的分析检测难度较大。该文对近年来环境水体中酚类EDCs的分析方法进行了综述,分别对样品前处理与检测分析技术进行了介绍,其中前处理技术包括样品萃取、样品净化和样品衍生化,检测分析技术包括化学分析和仪器分析。最后对酚类分析方法进行了展望。  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号