萃取-火焰原子吸收法测定河水中的Cr(Ⅵ)和Cr(Ⅲ)

铬被广泛应用于电镀、印染、制革及纺织等行业,是造成河水和土壤铬污染的主要原因。铬在河水中主要以Cr(Ⅵ)和Cr(Ⅲ)形式存在,其价态不同,毒性也不同。适量Cr(Ⅲ)为人体所必需,以维持正常的新陈代谢;而Cr(Ⅵ)则被证明由于其强氧化性和对皮肤的高渗透性可以通过皮肤接触引起皮肤的溃烂、发炎,甚至导致生物的癌变,所以必须对样品中的Cr(Ⅵ)和Cr(Ⅲ)进行分别测定。     

三正辛胺萃淋树脂在线分离富集原子吸收光谱法测定Cr(Ⅵ)

铬在自然界中主要以Cr(Ⅲ)与Cr(Ⅵ)形式存在.Cr(Ⅲ)是维持糖、脂肪及蛋白质代谢的必需元素~([1]).而Cr(Ⅵ)毒性较大,为致癌的有害物质~([2]).自20世纪50年代铬一直是人们关注的金属元素,不同价态铬化合物的环境化学性质、生物化学性质和毒性水平均有显著差异~([3]).因此,铬的价态分析对环境和医学研究具有重要意义.     

高效液相色谱-电感耦合等离子体质谱法测定玩具材料中六价铬

正我国是世界最大的玩具出口国,同时也是对欧盟出口玩具的大国。玩具中有害重金属元素会影响孩子的健康[1]。自然界中的铬具有不同的形态,主要是以三价铬[Cr(Ⅲ)]和六价铬[Cr(Ⅵ)]的形式存在。三价铬是人体维持健康的微量元素[2],Cr(Ⅵ)则具有较大毒性。美国环境保护局将Cr(Ⅵ)确定为17种高度危险的毒性物质之一。因     

流动注射分离-原子吸收光谱法测定底泥中生物可利用态Cr(Ⅵ)和Cr(Ⅲ)

湖泊底泥中生物可利用态铬是对湖泊生态环境最有影响的铬赋存形态,分别用弱有机酸或螯合缓冲剂对底泥中生物可利用态铬进行萃取分离。在流动注射系统中,分别以串联在流路中阴、阳离子交换微型柱分离,NH4NO3 抗坏血酸和H2SO4两种洗脱液同时逆向洗脱,实现了对底泥可利用态铬中Cr(Ⅵ)和Cr(Ⅲ)同时在线分离和原子吸收光谱法测定。交换时间2min,洗脱50s,Cr(Ⅵ)和Cr(Ⅲ)回收率分别为85.4%~94.8%和96.7%~106%。本方法对实际样品中不同价态铬进行测定,铬回收率可达95%。Cr(Ⅵ)和Cr(Ⅲ)的检出限和最大相对标准偏差分别为0.9μg/L、6.4%和2.7μg/L、3.5%。     

HPLC-ICP-MS联用技术应用于海产品中铬形态的分析

铬的工业用途很广,主要有金属加工、电镀、制革行业,这些行业排放的废水中的铬在水生生物体内富集~([1]),对海产品的质量带来巨大影响,损害人们的健康.环境中主要存在两种铬的形态,维持人体生命的必须元素Cr(Ⅲ)和具有高毒、强致癌性的Cr(Ⅵ)~([2]).因此,仅测定海产品中铬的总量已不能满足人们的需要,测定铬的形态十分有必要.     

荞麦皮生物吸附去除水中Cr(Ⅵ)的吸附特性和机理

农业废弃物荞麦皮作为生物吸附剂去除水中Cr(Ⅵ),研究了荞麦皮对Cr(Ⅵ)的去除动力学以及溶液pH、吸附剂用量和Cr(Ⅵ)初始浓度对去除效率的影响;通过FT-IR,XPS,SEM-EDX对荞麦皮表面组成和结构进行表征,探索荞麦皮去除Cr(Ⅵ)的机理.结果显示:荞麦皮对Cr(Ⅵ)有很高的去除效率.常温下5.0 g·L-1的荞麦皮在pH=2.0下对100 mg·L-1 Cr(Ⅵ)溶液的去除率可达99.87%.荞麦皮对Cr(Ⅵ)的去除率随溶液pH降低而升高,在pH=2.0时达到最大;随吸附剂用量增加而增大;随Cr(Ⅵ)初始浓度增加而减小.单位质量荞麦皮对Cr(Ⅵ)的去除量随吸附剂用量增加而减小;随Cr(Ⅵ)初始浓度增加而增加,最后趋于稳定.在20℃,pH=2.0,吸附用量为5.0 g·L-1时,荞麦皮对Cr(Ⅵ)的最大去除容量约为36.4 mg·g-1.荞麦皮吸附去除Cr(Ⅵ)的过程符合准二级吸附动力学.FT-IR,XPS和SEM-EDX分析结果表明:荞麦皮是一个多孔材料,表面存在羧基、氨基、羟基等活性基团;荞麦皮对Cr(Ⅵ)的去除是一个吸附-还原耦合的过程,包括Cr(Ⅵ)在荞麦皮表面上的静电吸附,以及此后的固相还原和对还原态的Cr(Ⅲ)再吸附;Cr(Ⅲ)的吸附主要是通过与荞麦皮表面的羧基、氨基的配位,以及与其中的阳离子发生离子交换作用实现的.     

湘江(长沙段)水中铬的形态分布及其迁移

研究了湘江水中铬的存在形态、分离方法和分析流程。用极谱催化法测定了江水中的总铬、总溶解铬、颗粒态铬、有机态铬、溶解无机铬、溶解无机态Cr(Ⅵ)、溶解无机态Cr(Ⅲ)。分析了不同季节里铬的存在形态及其迁移转化。结果表明溶解无机态铬是主要的存在形态,其中溶解无机态Cr(Ⅵ)较易转化成毒性较小的Cr(Ⅲ)。不同季节中铬的各形态的含量不同,其中颗粒态铬和有机态铬在夏季的含量较高,而其余各形态的铬在秋、冬两季的含量高于春、夏两季。江水对铬污染的自净能力较强,铬造成的污染的范围较小。     

光度测定微量铬(Ⅲ)及连续测定铬(Ⅵ)和铬(Ⅲ)的新法

目前分光光度测Cr(Ⅲ)的方法一般灵敏度不高(ε<5×10~4),且Cr(Ⅲ)的直接胶束增溶光度法为数尚少。Cr(Ⅲ)、Cr(Ⅵ)是环境分析的两个重要项目,但它们的同时或连续分光光度测定法尚少报导。本文旨在研究一种Cr(Ⅲ)的直接胶束增溶分光光度法及不同价态铬(Ⅲ和Ⅵ)的连续光度测定,并拟用于工业或环境样品分析。 (一)仪器和试剂 72型分光光度计:上海分析仪器厂。     

磷酸三丁酯萃取原子吸收光谱法测定微量Cr(Ⅲ)和Cr(Ⅵ)

常用的 APDC-MIBK 和 DDTC-MIBK 萃取原子吸收法一般只能测至十几个ppb 浓度的铬,且需在较高温度下进行萃取.本文报道一种用磷酸三丁酯(TBP)萃取原子吸收光谱法测定微量 Cr(Ⅲ)和 Cr(Ⅵ)的方法.实验表明,Cr_2O_7在盐酸介质中可与 TBP 形成 Cr(Ⅵ)-TBP-Cl-溶剂化合物,借此可测定0-0.25μg·ml~(-1)浓度范围内的 Cr(Ⅵ).若用 KMnO_4将平行试样中的 Cr(Ⅲ)氧化为 Cr(Ⅵ),测得总铬量,通过差减法即可算出Cr(Ⅲ)的含量.本法灵敏度高,准确度好.     

HPLC-ICP-MS法测定环境水样中Cr(Ⅲ)和Cr(Ⅵ)及方法在复杂基体水样适用性

基于高效液相色谱和电感耦合等离子体质谱联用技术,建立测定环境水样中Cr(Ⅲ)和Cr(Ⅵ)的分析方法。结果表明Cr(Ⅲ)和Cr(Ⅵ)质量浓度在1~100μg/L范围内线性良好,方法检出限均为0.07μg/L,不同浓度(2,50,90μg/L)测试相对标准偏差在1.1%~6.3%之间。所建立方法无需其他前处理就可用于高盐度水样中两种形态铬分离分析。C18固相萃取小柱可高效吸附废水样品中的有色物质,但对其中的Cr(Ⅲ)和Cr(Ⅵ)没有吸附,可用于废水样品脱色处理。     

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.