电感耦合等离子体质谱法分析大鼠血、毛发及脏器中铅浓度及同位素比值

建立了电感耦合等离子体质谱(ICP-MS)同时测定铅浓度及同位素比值的方法,并应用于染毒大鼠血、毛发及组织脏器测定,以考察大鼠体内铅浓度及同位素比值分布情况及染毒剂量对其的影响.标准物质牛全血铅浓度测定结果为(278±4) μg/L,在证书标准值(283±18)μg/L范围内;测定10 μg/L Pb标准溶液的RSD<...     

警惕儿童铅中毒

儿童玩具和学习用品的含铅量普遍较高。有报告表明 ,7种玩具表面油漆中含的可溶性铅已超过国际最高允许量。学生常用的铅笔 ,有 6类超标 ,含铅量最高的超标 4 12倍 ;课桌、椅的棕黑色油漆层超标 36 7倍 ;彩色蜡笔足以引起儿童铅中毒。有关专家指出 :正常人血液中不应含铅 ;儿童铅中毒诊断标准为血铅水平超过或等于 0 4 83μｍｏｌ/Ｌ。铅主要通过消化道和呼吸道进入人的体内 ,而铅往往最容易被儿童吸收。除了前面提到的那些铅污染源 ,还有含铅汽油的燃烧、含铅油漆的风化、工业污染等 ,都是铅尘的重要来源。一旦发生铅中毒 ,会有以下表现…     

胚胎期铅暴露对斑马鱼行为发育的影响

目的了解胚胎期铅暴露对斑马鱼胚胎及幼鱼行为的影响,以探讨铅的神经行为发育毒性。方法斑马鱼胚胎期暴露醋酸铅浓度分别为0、0.1、0.5、2.5和12.5μmol/L,观察24 hpf胚胎的自主运动,分析测试5 dpf幼鱼对光周期的刺激反应。结果各组胚胎自主运动观察结果依次为(5.22±1.02)、(6.25±1.46)、(6.12±0.92)、(5.46±0.92)、(4.62±0.81)次/min,与对照组比较,随着铅暴露浓度增加,胚胎自主运动次数呈高至低变化趋势,多组间差异有统计学意义(P0.05)。幼鱼活力也随着铅暴露浓度增加呈现由高至低变化,明亮期12.5μmol/L铅浓度组及黑暗期2.5μmol/L铅浓度组平均活力均较对照组显著降低(P0.05);12.5μmol/L铅浓度组亮转暗前后1 min活力改变量较对照组显著增高(P0.05),并且暗刺激后活力动态变化呈易激惹、易衰退状态。结论胚胎期铅暴露能影响斑马鱼胚胎自主运动及幼鱼活力状态,低浓度铅暴露以兴奋作用为主,高浓度铅暴露则呈现抑制作用为主,但其内在机制尚有待进一步研究。     

实验性铅染毒对大鼠体内锌,钙的影响

以0、200×10-6、500×10-6、1000×10-6含铅饮用水染毒大鼠，在4、8、12周分批处死动物，取血、尿及组织分别测定铅、锌、钙等元素。结果表明，染毒200×10－6动物在4周时即出现全身症状；血铅浓度随染毒剂量增加而增高；尿铅、锌、钙的排出三者呈平行关系，排出高峰在4周。高尿锌导致脑、睾丸、骨、胰腺等组织锌含量降低，说明锌在铅中毒的发生机制中起重要作用，实验为应用锌制剂预防和治疗铅中毒提供依据。高尿钙所致机体影响有待进一步研究。     

降铅冲剂对低水平铅暴露仔鼠血铅及脑铅的影响

目的:研究降铅冲剂对低水平铅暴露仔鼠血铅及脑铅的影响,为评价降铅冲剂的作用提供依据。方法:选用Wister大鼠仔鼠60只,体质量80~100 g,随机分成6组,每组10只,分别为空白组、模型对照组、EDTA对照组、降铅冲剂低剂量组、降铅冲剂中剂量组、降铅冲剂高剂量组;造模后开始给药,EDTA对照组给CaNa2EDTA注射液10(mg/kg)/d腹腔注射,降铅冲剂低、中、高剂量组分别予降铅冲剂5(g/kg)/d、10(g/kg)/d、20(g/kg)/d的剂量灌胃,空白组和模型对照组予等量蒸馏水灌胃,给药共30 d。用石墨炉原子吸收光谱仪测定仔鼠血铅、脑铅。结果:(1)染铅后,各染铅组的血铅水平与空白组比较都显著升高(P<0.001),经过30 d的治疗后,各治疗组的治疗后血铅水平均有不同程度下降,与模型对照组比较均有统计学意义。(2)染铅后,各染铅组的脑铅水平与空白组比较都显著升高(P<0.05),治疗后,各组脑铅与治疗前比较均显著升高,降铅冲剂低、中剂量组的脑铅与模型对照组比较显著下降。结论:降铅冲剂能显著降低低水平铅暴露仔鼠的血铅和脑铅含量,其综合疗效优于CaNa2EDTA。     

铜质水嘴中铅含量与析出量的相关性探讨

试验探讨铜质水嘴中铅含量与析出量的关系。对一系列含铅标准铜片按照GB/T 17219–1998《生活饮用水输配水设备及防护材料的安全性评价标准》要求进行浸泡试验,使用原子吸收光谱法或电感耦合等离子体质谱法检测浸泡液中的铅含量,再利用20个已知铅含量的铜质水嘴样品进行析出量的检测和验证。得到铜质水嘴中铅含量与析出量的关系。试验结果表明:大部分内腔有电镀层的铜质水嘴,铅析出量小于5.0μg/L;内腔无电镀层的铜质水嘴中铅含量小于0.5%时,铅析出量小于5.0μg/L,符合GB/T 17219–1998标准要求。     

环境铅暴露的指示器

许多研究表明 ,头发是检验环境铅暴露的理想指示器。Creason研究了美国纽约市环境污染程度不同的 3个社区居民发中微量元素与环境暴露的关系 ,发现发铅及其他 5种元素的含量均与环境介质中的含量呈显著正相关 ,儿童发铅与环境介质的关系 (P <0 0 0 5 )比成人 (P<0 0 1 )更为密切。Chatt (1 980 )对加拿大多伦多所做的研究表明 ,离工业区 1 0 0km的农村居民发铅含量 (9 6μg/g)远低于居住在离冶炼厂 5 0 0m内的居民 (2 5 3 μg/g)和市中心居民 (1 4 7μg/g)。乔文建 (1 989)对武汉某蓄电池厂、印刷厂工人 ,万伯键 (1 993 )对辽宁沈阳某…     

上海市区大气颗粒物(PM2.5)中铅、镉的分析测定和污染特征研究

以石英超细纤维滤膜采集上海市长宁区的大气颗粒物(PM2.5)样品,采用球磨机将滤膜研磨成细微颗粒,并以0.7％ Triton X-100作为分散剂,制备了稳定均一悬浮液,建立了一种简便、绿色、快速的悬浮液进样-石墨炉原子吸收法测定PM2.5中铅和镉的方法.铅在0.1～75 μg/L范围内,镉在0.2～3 μg/L范围内,校正曲线的线性相关性大于0.998;铅和镉的检出限分别为0.36和0.06 μg/L,相对标准偏差小于5％.采用HF-HN03体系酸消解样品,并与电感耦合等离子体质谱法和石墨炉原子吸收光谱法测试结果对比,验证了方法的准确性.采用本方法对2014年11月～ 2015年5月期间上海市区大气中PM2.5及铅和镉的污染特性进行分析,结果表明,铅和镉的质量浓度随时间变化趋势与PM2.5的质量浓度随时间的变化趋势呈现良好的一致性.     

急性铅染毒对小鼠行为及脂质过氧化水平的影响

为了解急性铅染毒对小鼠行为及脂质过氧化水平的影响,并探讨两者关系,将48只ICR小鼠随机分为4组,低、中、高铅组小鼠分别予以醋酸铅2、10、50 mg/kg ip染毒,隔日1次,连续3次;对照组予以等量的生理盐水;染毒后作自发活动、Morris水迷宫测试,实验结束时测定血浆、脑匀浆MDA和T-SOD。结果表明,铅染毒小鼠易激惹、多动,逃避潜伏期显著延长(P<0.01)。血浆MDA、T-SOD和脑匀浆MDA明显增高(P<0.01),并与染铅剂量呈正线性相关(P<0.01)。但小鼠行为改变与脂质过氧化水平之间关系不明显。结论是急性铅染毒能够影响小鼠的行为,呈现激惹、多动及学习记忆能力减退;急性铅染毒能提高小鼠脂质过氧化水平,并可代偿性提高机体T-SOD活性,但脂质过氧化水平增高是否为急性铅中毒行为改变的机制之一尚有待进一步研究。     

蚯蚓对土壤中8:2与10:2氟调醇的生物富集与转化

以蚯蚓(Eisenia fetida)为受试生物,研究了8:2和10:2氟调醇(FTOH)在蚯蚓体内的生物富集特性、清除速率和生物转化等.结果表明,全氟辛酸(PFOA)是8:2 FTOH主要的末端降解产物,全氟癸酸(PFDA)是10:2 FTOH主要的末端降解产物.暴露30 d后,蚯蚓体内的全氟化合物浓度达到最高,分别为PFDA(565 ng/g)8:2 FTOH(505 ng/g)PFOA(179 ng/g)10:2 FTOH(148 ng/g).清除阶段8:2 FTOH,10:2 FTOH,PFOA和PFDA半衰期(t1/2)分别为23.1 d,16.5 d,5.8 d和11.4 d,其对应的清除速率常数(ke)分别为0.03/d,0.042/d,0.12/d,0.061/d,说明长碳链的PFCAs更难从生物体内清除,母体化合物FTOHs在蚯蚓体内的持久性更强.     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.