激光剥蚀电感耦合等离子体质谱法测定地质玻璃中铅同位素组成

将193nm准分子纳秒激光与四级杆电感耦合等离子体质谱联用,测量了国际参照物玻璃中Pb同位素丰度比。通过剥蚀NIST612,USGS和MPI-DING玻璃,探讨了利用激光剥蚀电感耦合等离子体质谱直接测定固体样品铅同位素比值的精密度及其适用范围。通过扣除Ar载气中204Hg对204Pb的同量异位素干扰,采用内标法和外标法校正LA-ICP-MS仪器的质量歧视效应,获得的206Pb/204Pb、207Pb/204Pb、208Pb/204Pb同位素比值测量的相对误差小于±1.2%,207Pb/206Pb、208Pb/206Pb同位素比值测定的相对误差小于±0.8%。对比结果表明,采用内标法校正的结果更接近真实值。测定的Pb同位素比值的精密度与样品中Pb含量密切相关,对Pb含量大于40μg/g的样品,同位素比值206Pb/204Pb、207Pb/204Pb、208Pb/204Pb的RSD在1.0%以内,207Pb/206Pb、208Pb/206Pb的RSD在0.5%以内。大气颗粒物样品中Pb含量很高,采用LA-ICP-MS测定Pb同位素比值,能够鉴别污染来源,满足示踪的要求。     

应用多接收器电感耦合等离子体质谱法测定海洋碳酸盐中稳定铅同位素组成

研究了多接收器电感耦合等离子体质谱仪(MC-ICP MS)测定铅同位素比值时,影响测试结果准确度和精密度的主要因素及其优化过程。在优化条件下,10 h内连续30次测定4 ng/mL NIST SRM 981同位素标准溶液铅同位素比值,获得208Pb/206Pb、207Pb/206Pb和206Pb/204Pb相对标准偏差(RSDs)分别为0.005%、0.004%和0.054%。长期监测208Pb/206Pb、207Pb/206Pb和206Pb/204Pb,标准偏差(2SDs)分别为0.000 06、0.000 05和0.006 7。采用NEPTUNE MC-ICP MS法测定了低铅海洋碳酸盐样品中稳定铅的同位素比值,并对南海橙黄滨珊瑚(Porites lutea)和库氏砗磲(Tridacna gigas)进行了分析,得到全流程空白为8～10 pg,重复样误差优于0.1%。经0.50 mol/L HNO3洗脱之后,得到海南珊瑚样品中208Pb/206Pb、207Pb/206Pb的比值分别为2.086 2±0.001 5、0.849 90±0.001 47(n=16);海南砗磲样品中208Pb/206Pb、207Pb/206Pb的比值分别为2.116 9±0.004 2、0.864 81±0.001 62(n=9)。进一步考察了南海海洋碳酸盐中204Pb的同位素比值。分析结果表明,南海海洋碳酸盐中稳定铅同位素比值与中国气溶胶、珠江三角洲大气沉降、黄土及南海海底玄武岩等具有很好的相关性。方法适用于复杂基体高钙低铅的海洋碳酸盐样品中铅同位素比值的分析。     

电感耦合等离子体质谱法测定水泥样品中的铅同位素比值

研究和讨论了用电感耦合等离子体质谱仪(ICP—MS)测定铅的同位素比值测定时，影响测试结果的准确度和精密度的主要因素及其优化过程。在优化后的仪器分析条件下，测定5μg/L的NIST SRM981自然丰度铅同位素标准溶液的各对铅同位素比值，获得的^207Pb／^206Pb分析精度可优于0．1％。在该条件下测定了14个不同的水泥粉样品中的铅同位素比值，结果显示：铅的同位素比值分析技术可以用来示踪环境监测样品的铅污染源。     

激光烧蚀-多接收电感耦合等离子体质谱测定铀颗粒物中铀全同位素比值

建立了铀颗粒物中铀全同位素比值的分析方法,采用双面胶带装载铀颗粒物样品,优化激光烧蚀-多接收电感耦合等离子体质谱的运行参数,用标准样品交叉法校正质量分馏和探测器检测效率,测定了粒径几十微米的铀标准物质CRM124-1、GBW04234和GBW04238中铀全同位素比值.本方法对铀颗粒物中235U/238U、234 U/235U和236 U/235U测量的相对实验标准不确定度分别小于0.050％,1.7％和1.8％,测量结果与参考值在不确定度范围内符合.研究表明,本方法可快速、准确、高精度地测定铀颗粒物中铀全同位素比值.     

ICP-MS测定土壤中铅同位素比值及地域差异性比较

建立用HNO_3-H_2O_2-HF体系微波消解前处理样品,利用电感耦合等离子体质谱测定土壤中铅同住素比值的方法,探讨并优化了影响测试结果的两种干扰因素.该方法中~(207)Pb/~(206)Pb和~(208)Pb/~(206)Pb的短期测量稳定性RSD分别达到0.12%和0.13%,长期测量的偏差分别在0.002和0.01以内,样品测量的最佳范围是10～40μg/L.采用标样-样品交叉法测定了湖南、湖北、云南、贵州、河南、福建、辽宁7个省的48个地区土壤中的铅同位素比值,结合聚类分析和主成分分析比较了各省土壤中同位素分布的差异,初步探讨了利用~(207)Pb/~(206)Pb和~(208)Pb/~(206)Pb比较烟叶产区的可能性.     

土壤及其他背景样品中铅同位素比值的测定方法

为给铅同位素示踪技术在判别土壤、大气、水体和人体中铅与相关重金属污染来源,区别汽车尾气铅污染和工业铅污染等方面的应用提供科学依据。通过大量的对比条件实验,拟出了土壤、煤、汽车尾气和气溶胶样品中铅同位素比值的测定方法。利用这三个流程分别测定了采自杭州茶园的土壤及茶园附近的煤、汽车尾气和气溶胶样品的铅同位素比值,其中207Pb/206Pb的精度(2σ)均优于±0.03%。重复样误差优于±0.05%2。08Pb强度一般均在1V以上,有的高达8 V以上。监控分析流程的国际标准物质NBS981的207Pb/206Pb为0.91449±0.00004。全流程本底铅为10-8数量级。     

多接收电感耦合等离子体质谱在单个铀颗粒物分析中的应用研究

为准确地获取单个铀颗粒物中具有核保障监督和核取证意义的铀同位素组成信息和~(230)Th/~(234)U比值,本研究基于多接收电感耦合等离子体质谱(MC-ICP-MS),建立了不同粒径铀颗粒物中铀同位素比值的测量方法和不经化学分离纯化流程的~(230)Th/~(234)U分析技术。在评估铀钍本底的基础上,采用外标法校正同位素的质量分馏效应,进样0.40 ng/g的天然铀工作溶液跳峰测量离子计数器检测效率,使用已知铀钍比例的标样校正铀钍响应差异,完成分析方法的不确定度评估。结果表明,化学处理过程引入的~(238)U和~(232)Th分别小于8×10~(-5)ng和1.5×10~(-3)ng,MC-ICP-MS对粒径0.5~5.0μm铀颗粒物中~(235)U/~(238)U测量的相对扩展不确定度3.6%(k=2),主要来自本底扣除引入的不确定度和B类不确定度;对粒径5μm铀颗粒物中~(235)U/~(238)U测量的相对扩展不确定度0.2%(k=2),主要来自法拉第杯检测器对弱信号测量的不确定度;对更大粒径铀颗粒物中~(234)U/~(235)U和~(236)U/~(235)U测量的相对扩展不确定度分别小于3.5%和3.8%(k=2),主要来自B类不确定度。不经铀钍分离纯化流程,MC-ICP-MS可测得粒径几十微米铀颗粒物中~(230)Th/~(234)U比值信息,并诊断浓缩铀颗粒物生产年龄。     

电感耦合等离子体质谱法测定动物组织中的铅同位素比值

动物组织样品1.000 0g用高氯酸1mL和硝酸10mL经加热消解处理,采用电感耦合等离子体质谱法测定样品溶液中的铅同位素比值。连续6次测定一个动物组织样品,204 Pb/206Pb、207Pb/206Pb和208Pb/206 Pb比值的相对标准偏差分别为0.23%,0.090%,0.14%。测定了20个鸡样品和20个猪样品,结果表明:鸡样品的上述3个比值依次在0.052 1~0.060 2,0.829 4~0.920 4,1.990 3~2.203 7之间;猪样品的上述3个比值依次在0.050 1~0.059 6,0.820 9~0.918 0,1.999 4~2.242 3之间。     

基于铅同位素的有机猪肉溯源研究

采用不同的饲养方式,利用ICP-MS分别对有机猪肉和普通猪肉中的铅同位素比值进行测定。方差分析结果表明,铅同位素比值~(204)Pb/~(206)Pb,~(207)Pb/~(204)Pb,~(208)Pb/~(204)Pb,(~(207)Pb/~(208)Pb)/~(204)Pb,~(208)Pb/~(207)Pb/~(204)Pb具有显著性差异(P0.05),利用主成分分析和聚类分析等,得到相应的判别模型,该模型的初始分组正确率为100.0%,交叉验证正确率为85.0%。方法对有机猪肉能够有效溯源识别。     

激光剥蚀-多接收电感耦合等离子体质谱法 测定含钚颗粒物中240 Pu/239 Pu比值

为高精度、准确地获取含钚颗粒物中具有核保障监督意义和核取证价值的钚同位素比值,建立了激光剥蚀-多接收电感耦合等离子体质谱(LA-MC-ICP-MS)测定含钚颗粒物中240 Pu/239 Pu的分析方法.采用检漏、安装排风罩和擦拭剥蚀池内壁等方式有效降低激光剥蚀产物沾污实验室和危及人身安全的潜在风险.联用扫描电迁移率粒径谱仪(SMPS)与激光剥蚀-多接收器等离子体质谱(LA-MC-ICP-MS)研究了激光剥蚀玻璃基体标样产生气溶胶的分布特性,结果表明,剥蚀产物的主要粒径是40~500 nm,应尽量采用水平管道连接激光剥蚀进样系统与MC-ICP-MS,含钚颗粒物分析后剥蚀池持续吹扫时间应大于15 min.采用外标归一化法离线校正质量分馏效应和离子计数器检测效率,建立了含钚颗粒物中240 Pu/239 Pu的LA-MC-ICP-MS分析方法,固定束斑直径30μm、脉冲重复率5 Hz、剥蚀时间5 s,调节能量密度使含钚颗粒物模拟样品中239 Pu的信号强度分别达2×104 cps和2×105 cps,本方法对240 Pu/239 Pu测量的相对实验标准不确定度小于1.4%(n=6),测量结果与参考值的相对偏差小于4.7%,仪器调试时间和单个样品测量时间分别为9.0和0.5 h.含钚颗粒物模拟样品分析结果表明,本方法精度高、结果准确、分析速度快,可满足核保障监督、禁产核查和核取证中含钚颗粒物直接分析的需求.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.