固相萃取-高效液相色谱法同时测定环境水体中微量药品和个人护理用品

结合固相萃取与高效液相色谱分析技术,建立了一种可以同时检测环境水体中10种微量药品和个人护理用品(PPCPs)的分析方法。将水样pH调节至5,过Poly-Sery HLB固相萃取小柱,用6mL的甲醇洗脱。洗脱液在Agilent Eclipse XDB-C18色谱柱上分离,以水-乙腈为流动相进行梯度洗脱,检测波长为224nm。10种目标化合物的质量浓度在0.5~20mg·L-1范围内与其峰面积呈线性关系,方法的检出限(3S/N)为6.0~54.6μg·L-1,测定下限(10S/N)为20.1~182.1μg·L-1。对自来水和地表水进行加标试验,回收率分别在71.2%~108%和56.7%~97.6%之间。方法用于某城镇污水处理厂的原水和最终处理出水的检测。     

超高效液相色谱-三重四极杆质谱联用同时检测环境水体中22种典型药品及个人护理用品

应用超高效液相色谱-三重四极杆质谱联用仪(UPLC-MS/MS)建立了环境水体中22种典型药品及个人护理用品(pharmaceuticals and personal care products, PPCPs)的分析方法。通过对固相萃取柱、淋洗液、色谱流动相等的优化,确定以Oasis HLB小柱为固相萃取柱、甲醇为淋洗液、水(0.1%甲酸)-甲醇(7:3, v/v)为流动相进行水样预处理和色谱分离。在最优条件下,目标物在水中的回收率为73%~125%,相对标准偏差(RSDs)为8.8%~17.5%。各目标物的线性范围均为2~2000 μg/L,线性相关系数(R²)不小于0.997。该方法具有检出限低、回收率高等优点,经实际样品测试,适用于环境水体中22种典型PPCPs的同时检测,可为微量有机物引起的水环境风险评价和控制的相关研究提供支持。     

荧光摩尔吸收系数法测定洗护用品中烷基酚聚氧乙烯醚

建立了洗涤用品和化妆品护理用品中烷基酚聚氧乙烯醚(NPnEO和OPnEO,n=0～30)的高效液相色谱分析方法。采用乙腈水溶液超声提取不同基质类型的洗涤用品和化妆品护理用品,利用快速反相C18柱(Poroshell 120 EC-C18,75 mm×4.6 mm,2.7μm)串联HILIC硅胶色谱柱(Atlantis HILIC Slica,250 mm×4.6 mm,5μm)对NPnEO和OPnEO的各单体及样品杂质进行有效分离,以乙腈-10 mmol/L醋酸铵溶液为流动相进行梯度洗脱,荧光检测器进行检测,建立了荧光摩尔吸收系数定量校正NPnEO和OPnEO的计算模型。通过测定NPnEO和OPnEO混合标准溶液,计算得到两者的荧光摩尔吸收系数。对样品中NPnEO和OPnEO的平均分子量进行测定,并利用荧光摩尔吸收系数对总峰面积进行校正定量。方法的回收率为99.0%～105.7%,相对标准偏差不大于12.5%,定量下限为40.0 mg/kg。该方法快速、准确、适用范围广,可用于各类洗涤用品和化妆品护理用品中烷基酚聚氧乙烯醚(NPnEO和OPnEO)含量的检测。     

硫酸改性聚(甲基丙烯酸缩水甘油酯-乙二醇二甲基丙烯酸酯)固相微萃取涂层-高效液相色谱检测水中4种药品及个人护理用品

多巴胺修饰的不锈钢丝表面原位合成得到聚(甲基丙烯酸缩水甘油酯-乙二醇二甲基丙烯酸酯)(poly(GMA-EGDMA))材料,经硫酸改性后作为固相微萃取涂层,建立检测水样中4种药品及个人护理用品(PPCPs)的固相微萃取-液相色谱联用分析方法。在优化实验条件下取3 mL水样调节至pH 5.5,在30℃下,搅拌萃取60 min,乙腈-0.1%甲酸(25∶75,V/V)解吸30 min后,HPLC进样分析,实验结果表明,该涂层材料对4种PPCPs具有较好的萃取效果,2~200μg/L浓度范围内线性关系良好,相关系数均大于0.997,方法检出限(S/N=3)范围为0.5~5.0μg/L,相对标准偏差在4.1%~11.9%之间;加标实验回收率为70.6%~105.5%。本方法前处理简单、绿色环保、回收率高、精密度好,可用于实际水样中4种PPCPs的检测。     

含钆对比剂的环境污染现状、毒性及分析方法

随着医疗技术的发展,药品和个人护理产品(PPCPs)因其在全世界范围内的大量使用,受到了越来越多的关注,含钆对比剂(GBCAs)可归属于这类化学品.许多造影剂在医疗诊断中被广泛使用以提高医学成像质量,大量的造影剂经生产、使用等过程释放至环境,成为新型环境污染物,对环境及生态造成影响,其中含钆对比剂便是其中一大类.GBC...     

静电场轨道阱质谱在水质污染物检测中的应用

静电场轨道阱质谱(Orbitrap MS)是一种高分辨(HR)MS。由于其相对傅里叶变换-离子回旋共振(FT-ICR)MS更高的性价比,近些年来在世界各地得到了广泛的推广和应用。特别是将其与超高效液相色谱(UHPLC)联用,UHPLC-Orbitrap MS作为一种定性定量工具,显示出了强大的分析能力,给复杂环境样品分析带来了新的机遇。近些年来,将其应用到自然水体及污水中药物、激素、抗生素、农药、个人护理用品等一系列特定痕量污染物和复杂溶解性有机质(DOM)的分析中,该方法分析速度快、灵敏度高、重现性好,可同时满足复杂样品扫描分析和单一化合物精准鉴定的要求。高质量精度让碎片离子或转化离子与母离子之间的关联分析变得简单易行,且多级质谱(MS~n)可用来对未知化合物进行结构解析,使得该方法可用于污水处理过程中化合物转化路径的研究。一系列前期探索表明了该技术在水质分析方面有着更广阔的应用前景。     

冷冻干燥技术在环境水样有机新污染物前处理中的应用进展

有机新污染物是一类在先进分析技术帮助下新鉴定的、现有法规未管制的、人为源的有机污染物.有机新污染物主要包括药品与个人护理、农药、全氟化合物、内分泌干扰物等,其会产生内分泌干扰效应、诱发抗性基因传播,还对人类和野生生物的生存与发展构成潜在威胁,因此检测环境样品中的有机新污染物浓度对生态环境和人体健康具有重大意义.由于环境...     

引言

新型污染物（emerging pollutants）是指对生态环境具有潜在危害但环境监测部门尚未开展常规监测的污染物。与传统的污染物相比,新型污染物组成复杂,如短链氯化石蜡具有近万种同类物(congeners),复杂环境介质中微量/痕量新型污染物的准确定性和定量仍是具有很大挑战的技术难题。多种色谱技术,尤其是色谱与质谱的联用技术是新型污染物检测的有效手段。
我国环境科学工作者在新型污染物检测技术开发方面取得了很大进展,达到了国际先进水平。为反映我国新型污染物检测技术研发成果,推动新型污染物相关研究,我们邀请了相关科研机构、高校以及环境监测部门的专家撰稿,在"新型污染物色谱分析专栏"集中报道新型污染物检测技术的最新研究成果。本专栏论文不仅有药品及个人护理用品（PPCPs）、全氟化合物、短链氯化石蜡等国内外高关注的新型污染物色谱分析新方法,而且还有目前社会各界普遍关心的雾霾有害成分解析技术与方法。相信本专栏所报道的新技术和新方法对读者会有所帮助和启发。     

深共熔溶剂-高效液相色谱联用提取测定环境水样中的3种药品和个人护理品

建立了深共熔溶剂-高效液相色谱联用提取测定环境水样中3种药品和个人护理品(PPCPs)的方法。通过优化前处理条件,3种PPCPs(氯霉素、氯苯甘醚和萘普生)利用氯化胆碱-乙二醇深共熔溶剂为提取剂,经超声功率120 W下超声波提取5 min,离心转速9000 r/min下离心10 min富集提取。采用外标法定量分析,在5.0~200.0 mg/L范围内线性关系良好,相关系数r≥0.9998。3种环境水样中PPCPs的回收率为81.4%~94.8%,相对标准偏差分别为1.5%,0.4%和0.3%。氯霉素、氯苯甘醚和萘普生的方法检出限(LODs)分别为0.9,3.3,1.6 mg/L,定量限(LOQs)分别为3.1,12.2,5.0 mg/L。方法能够满足环境水样中3种PPCPs的检测需求。     

基于超高效液相色谱-高分辨质谱技术的水中112种药品和个人护理用品的高通量筛查和定量方法

采用超高效液相色谱-三重四极杆/静电场轨道阱高分辨质谱法（UHPLC-Q-Orbitrap MS）,建立了水中112种药品和个人护理用品类污染物（PPCPs）的快速筛查及定量分析方法。水样分别在酸性及碱性条件下提取,分别经SPE柱净化,以UHPLC-Q-Orbitrap MS进行分离检测,采用全扫描/数据依赖二级扫描（Full MS/dd-MS²）模式进行扫描,实现了水中112种PPCPs的定性筛查,并基于一级母离子峰面积对其含量进行了定量检测。112种PPCPs的定量限为0.002~0.8 μg/L,在各自的线性范围内均呈良好的线性关系（r²≥0.9901）; 3个水平（0.2、0.4、0.8 μg/L）下的添加回收率为60.1%~129.5%,相对标准偏差为1.1%~17.8%（n=6）。将所建立的方法用于来自大连市7个区的水样中PPCPs的筛查,共筛查出16种污染物,并对其进行了定量分析。本方法简单快速,灵敏度高,筛查范围广,为水质的管理和环境风险监测提供了一种有力的技术手段。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.