人牙齿中锶的特效树脂分离及其同位素测定

采用锶特效树脂(Sr-Spec)建立了快速分离富集人牙齿中微量元素锶,并测定87Sr/86Sr的有效方法。采用HNO3-HClO4体系消解牙齿样品,以8mol/L HNO3为介质上柱,8mol/L HNO3淋洗,0.05mol/LHNO3洗脱,收集淋洗液,蒸干;采用正热电离质谱法进行87Sr/86Sr的测定。结果表明,利用Sr-Spec树脂,不仅能将锶与基质中大量钙分离,并能有效分离同位素测定中干扰元素铷。本方法可以缩短分离时间,提高分离效率,减少试剂用量,降低实验空白。采用本方法对陕南地区人牙齿牙釉质中锶进行分离,测得的87Sr/86Sr值在0.710948～0.711037之间。     

利用锶特效树脂分离富集岩石样品中的锶及测定~(87)Sr/~(86)Sr

本研究以Sr-Spec树脂作为分离锶的特效树脂,以HNO3为淋洗液,通过改变HNO3的浓度,将地质岩石样品中的锶分离富集.实验结果表明,Sr与基质元素和Rb能很好地分离.利用Sr-Spec树脂分离国际标准物质SRM607、日本岩石标样JA-2、JB-2、JF-2和国家标准物质GBW04111后, 测得同位素比值87Sr/86Sr结果及误差(2σ)分别为1.200660±22, 0.706350±17, 0.703640±16, 0.709692±22和0.700008±23.相对于常规的阳离子树脂分离方法,此方法所用淋洗试剂量少,分离流程短,可以降低实验空白并提高工作效率.因此,Sr-Spec树脂分离法是快速分离富集不同岩性地质样品的Sr并测定87Sr/86Sr的有效方法.     

多接收等离子质谱高精度测定现代人齿中Mg同位素

Mg是构成牙齿重要组分,其含量和同位素组成可记录居民生活地域、饮食习惯以及口腔健康信息等重要信息.本研究建立了高精度多接收等离子质谱(MC-ICP-MS)测定牙齿中Mg同位素方法.牙齿样品经微波消解仪消解,后采用AG50W-X8阳离子树脂分离溶液中的Mg元素,以1 mol/L HNO3为介质上柱,40 mL1 mol/L HNO3洗脱Na+等杂质离子,再以30 mL 1 mol/L HNO3收集Mg元素,60 mL 1 mol/L HNO3洗去其它杂质,蒸干Mg收集液.MC-ICP-MS进行Mg同位素组成测定.MC-ICP-MS仪器自身的质量分馏利用“样品-标准”交叉技术(“Sample-standard”bracketing technique)解决.实验结果表明,利用AG50W-X8阳离子树脂,可在保证Mg回收率的情况下,将牙齿样品中的Mg和其它基质元素彻底分离,且不造成同位素分馏.采用此方法对现代人离体牙牙釉质中Mg同位素进行分离测定,牙齿的δ25Mg在较大的范围变化(-1.38‰ ～4.59‰).本方法为利用人牙齿中Mg同位素研究Mg的暴露水平、环境污染等信息提供重要的实验和理论依据.     

高铷/锶比地质样品中锶的共沉淀法快速分离及其高精度同位素测试

高铷/锶(Rb/Sr)比地质样品Sr同位素的分析测试中,利用NaOH对样品进行共沉淀处理可有效去除Na、K等基体元素和对Sr测试产生同质异位素干扰的Rb。通过对反应温度、时间、碱浓度等条件进行优化,确立了最佳反应条件。结果表明,以2 mL 5%(w/V) NaOH为沉淀剂,100℃反应1 h,可去除99%以上的Rb、Na、K和Al, Sr回收率优于96%。共沉淀反应后,利用AG50W×12阳离子交换树脂仅需进行一次过柱分离即可获得高纯度Sr。NaOH(99.99%)经过纯化后用于共沉淀反应,不会引入基体元素,Sr的流程空白小于182 pg。对8种不同Rb/Sr比的岩石标准样品(JR-2、BCR-2、BHVO-2、W-2、AGV-2、JG-3、JA-3、GSP-2)进行分离,结合高灵敏度热电离质谱仪(TIMS)获得高精度Sr同位素比值。结果表明,共沉淀-阳离子交换树脂分离流程具有适用范围广且稳定可靠的优点,同时可节省大量无机酸,且耗时较短。通过共沉淀法预富集Sr,为高Rb/Sr比地质样品的Sr同位素测试提供了一种新的分离途径,具有重要的应用价值。     

阴离子交换树脂分离富集/电感耦合等离子体质谱测定珊瑚中铅的同位素组成

在自制微型离子交换柱的基础上,建立了阴离子交换树脂AG1-X8分离富集珊瑚中痕量元素Pb的前处理方法,并使用高分辨电感耦合等离子体质谱(HR-ICP-MS)测定了海南橙黄滨珊瑚(porites lutea)样品中的Pb同位素比值。从全程空白值、洗脱曲线、回收率和基体分离情况等方面考察了不同洗脱剂的洗脱效果,结果表明,采用0.50 mol/L HNO3时的洗脱效果最好,方法的全程空白值为18 pg,Pb的回收率为99.6%,在洗脱过程中无拖尾现象,且能与Ca、Sr、Mg、Fe、Mn、Zn、Ba和U等珊瑚中的基体元素成功分离,对上述基体元素的去除率均能达到99.8%以上。使用该方法测得海南珊瑚样品中的207Pb/206Pb、208Pb/206Pb比值分别为0.850 5、2.087 0,相对标准偏差(RSDs,n=21)分别为0.12%和0.11%。该法质量控制良好,表明建立的AG1-X8阴离子交换树脂分离富集/HR-ICP-MS测定珊瑚中Pb的同位素组成的方法可靠,可推广应用于其它复杂样品中铅同位素组成的测定。     

红酒中的~(87)Sr/~(86)Sr同位素比测定

研究了多接收电感耦合等离子体质谱(MC-ICP-MS)测定红酒样品中87Sr/86Sr同位素比的分析方法,并用建立的分离测定方法参加了欧洲参考物质与测量研究所(IRMM)组织的CCQM-P105国际比对,即红酒中87Sr/86Sr同位素比的分析比对.红酒样品经微波消解后,采用Dowex 50W×8树脂分离纯化锶,用MC-ICP-MS精确测定锶组分中的87Sr/86Sr同位素比,同时对测量结果的不确定度进行了分析和评定.     

TODGA树脂小柱分离-多接收电感耦合等离子体质谱（MC-ICP-MS）法测定岩石样品中Nd同位素比值

通过改进岩石样品分析物Nd的化学分离,实现Nd同位素比值的准确分析,为研究青藏高原岩石成因,揭示物质来源提供技术支持。采用TODGA萃淋树脂分离基体及其与Nd相邻的稀土元素,多接收电感耦合等离子体质谱（MC-ICP-MS）法测定Nd同位素比值,建立了简捷实用的地质样品Nd同位素分析方法。样品HF-HNO3分解, HNO3(3 mol/L )- H3BO3(0.12 mol/L)提取,上柱后,先用6 mL HCl(2.8 mol/L)淋洗干扰轻稀土,再用6 mL HCl(2.2 mol/L)淋洗分析物Nd,Nd淋洗液由MC-ICP-MS测定其同位素比值。分析国际岩石标准物质BCR-2、BHVO-2和AGV-2,所得143Nd/144Nd同位素比值（平均值 ± 2σ）分别为0.512638 ± 0.0000007、0.512990 ± 0.0000012和0.512792 ± 0.000016,这些同位素数据在误差范围内,与推荐值和文献值完全一致。方法适合各种类型地质样品,为西藏不同地区不同岩石提供了可靠的Nd同位素分析数据。     

电感耦合等离子体质谱(ICP-MS)法测定水产品中锶同位素比值

为推动锶同位素在水产品溯源中的应用,本文建立了基于电感耦合等离子体质谱法（ICP-MS）测定水产品中锶同位素比值的分析方法。水产品组织经冻干研磨和微波消解后,用ICP-MS测定样品溶液中的锶同位素比值,并采用标准品-样品-标准品交叉测量方法降低质量歧视效应的影响。结果表明,通过稀释样品消解溶液,将总锶浓度控制在70-100 μg/L,并与80 μg/L的锶同位素标准品溶液进行交叉测量,可准确校正质量歧视效应;84Sr/86Sr、87Sr/86Sr和88Sr/86Sr的日内精密度分别为0.06%、0.03%和0.03%,日间精密度分别为0.08%、0.04%和0.03%;按照所建立的方法测定大虾和扇贝生物成分分析标准物质的锶同位素比值,84Sr/86Sr、87Sr/86Sr和88Sr/86Sr的相对标准偏差均低于0.1%。该方法前处理简单快捷并且测量精密度高,可为锶同位素比值测定并进一步应用于水产品溯源研究提供技术支撑。     

地质样品铁同位素自动固相萃取系统研究

研发了一种自动固相萃取系统,用于分离地质样品中铁同位素。系统有4个并行通道,可以一次处理4个样品。对于这4个样品,一次处理过程仅需24 min。选用AG1-X8阴离子交换树脂对花岗岩样品(GBW07103)中的铁进行萃取。在萃取过程中,当盐酸浓度大于6 mol/L时,铁形成络阴离子并被吸附在AG1-X8阴离子交换树脂上,其余阳离子被洗脱出来。用浓度为8 mol/L的HNO 3和H 2O洗脱铁,铁的洗脱体积为4 mL,铁可以被定量回收,回收率达到96.0%~107%。消除了测试过程中的基体影响,提高了样品处理效率,减少了人为污染风险,是一个多元化样品处理工具。     

阴离子交换树脂分离同位素稀释等离子体质谱法快速测定地质样品中的铼

建立了适合大批量低含量Re地质样品的测定方法,0.2 g样品通过HF,HNO3分解后在2 mol/L的HCl介质中用阴离子交换树脂进行振荡吸附,然后用HNO3(1+1)解脱,同位素稀释等离子体质谱法测定。     

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.