《实验室溶液制备手册》新书出版

化学测量是科技创新、国民经济发展、国际贸易的重要技术支撑。准确可靠的分析测量结果与环境保护、公共安全、科技发展、人民健康、国家声誉等密切相关。《实验室溶液制备手册》是各行业化学和分析实验室必备的工具书。该手册包含四部分内容：（1）溶液配制的基础知识、量器具校准、溶液和化学试剂、计量单位、有效数字及不确定度评定等；（2）无机分析、有机分析及容量分析的标准溶液的配制，共计1525种；（3）非标准溶液的制备，包括常用酸碱溶液、盐溶液、有机溶液、生化分析用溶液、缓冲溶液及指示剂溶液等；（4）附录，列出了溶液配制必要的常备及辅助信息或知识、化学试剂标准目录、国家一级和二级溶液标准物质目录及相关的技术规范、分子吸收分光光度法通则和化学试剂电位滴定发通则等。     

甲酸还原银氨溶液实验条件的改进

甲酸还原银氨溶液的实验,已有几篇文章论及。现将笔者多次试验的结果介绍如下。 1.试剂 5%AgNO3溶液稀氨水（1:4） 甲酸浓溶液（～80%） 2.配制银氨溶液取约5ml5%AgNO3溶液于一支洁净试管里,滴加稀氨水（1:4）,边加边振摇,至黑色沉淀恰好溶解为止,溶液的pH值近于11。     

配制硅酸溶胶的简易方法

胶体性质实验中的硅酸溶胶必须是;澄清、透明的液体,受热或注入盐酸时均应生成凝胶;若与氢氧化铁溶胶混合,立即凝聚。我的简易配制方法是：61％硅酸钠溶液（约0．54mol／L）与10．5％盐酸（约3mol／L）技体积比4：1混合制得硅酸溶胶。1．配制治波门）新制已1％硅酸钠溶液。将N：。a＊。·9＊。o和水按质量比1：6混合,微微加热、搅拌,使其完全溶解。（2）105％盐酸：将37％盐酸和水饺体积比1：3混合即得。2·制备硅镁溶胶选用口径小而相同的两支胶头滴管。向洁净试管中滴加30滴61％硅酸钠溶液,再改滴7～8滴10．5％盐酸,同时振摇试…     

醋酸铬(Ⅱ)水合物制备实验的新设计

通过多次探究和实践,对醋酸铬（Ⅱ）水合物制备实验进行了创新设计,新的设计采用在封闭的氢气气氛中手动倾析使Cr2+溶液进入醋酸钠溶液。与传统制备方法相比,该实验方法操作简单易行,产品纯度和产率高,是一种更为适合学生实验的制备途径。     

硫酸亚铁溶液的制备与性质实验的再改进

由于Fe2+极易被空气中的氧气氧化,故通常情况下配制的Fe2+溶液和在敞开环境中进行的性质实验都无法达到预期效果。经探究,优化了F2+溶液的制备方法并对其性质实验进行改进,收到了良好的效果。实验充分体现了简约性、微型化的设计理念,实现了废物的再利用。     

玻璃夹缝里的反应——氢氧化亚铁的制取

实验步骤称取FeSO4•7H2O晶体约5克（应是淡绿色）,用蒸馏水配制为5%左右的硫酸亚铁溶液。放入一、二枚光亮铁钉,并滴入几滴稀H2SO4溶液。塞紧瓶盖,备用。     

聚醚砜-羟基磷灰石混合溶液的流变性能

采用N,N-二甲基乙酰胺（DMAc）为溶剂配制含羟基磷灰石（HAP）的聚醚砜（PES）溶液,研究了PES-HAP-DMAc体系的流变曲线以及HAP的质量分数、混合溶液温度等对流变性能的影响。结果表明：混合溶液的非牛顿指数（n）随着温度的升高、HAP质量分数的增大而降低,表现为非牛顿流体。     

电感耦合等离子体质谱(ICP-MS)法测定高钨基体样品中稀土元素的含量

准确测定钨矿和钨酸盐晶体等高钨基体样品中稀土元素的含量有助于开展矿床地球化学特征研究及钨酸盐激光晶体材料的制备和性质研究。在高钨基体样品电感耦合等离子体质谱法（ICP-MS）分析时,为了考察高钨及高含量阳离子等基体组成对分析结果的影响,实验针对Na2WO4、CaWO4、NaY(WO4)2、MnWO4和(Fe,Mn)WO4等高钨基体样品,采用硝酸和氢氟酸高压密闭消解,加入稀土元素并用2% HNO3溶液稀释定容配制成稀土元素浓度为1 ng·g-1的基体匹配标准溶液;同时,直接用2% HNO3溶液配制稀土元素浓度相同的非基体匹配标准溶液以对比系统考察两种基体溶液中稀土元素的相对灵敏度系数（RSC）差异。结果显示,基体匹配溶液与2% HNO3溶液中稀土元素的RSC相对偏差基本小于15%,表明基体效应的影响可以忽略不计。进而,为了准确测定常见高钨基体样品中稀土元素的含量,实验建立了基于ICP-MS的高钨基体样品中稀土元素准确定量分析方法,该方法线性关系好（R2 ? 0.9997）,检出限低（0.5 ~ 27.9 pg·g-1）,准确度理想（相对误差-6.25 ~ 10.74%）。采用该方法测定了钨酸钙单晶实际样品中稀土元素的含量并将其与基体匹配法的测定结果进行比对,结果显示两者相对偏差为0.80 ~ 12.75%,说明本文所建立的分析方法可靠,能用于定量测定高钨基体样品中稀土元素的含量。     

粘度法研究明胶在聚氨酯弹性体表面的吸附

根据文献以异佛尔酮二异氰酸酯（IPDI）为原料制备了具有较好机械性能的聚氨酯弹性体胶条（PU）,并在胶条表面接枝肝素,得到肝素化聚氨酯胶条（PU-Hep）。将聚氨酯胶条浸泡在明胶稀溶液中,测量溶液粘度随时间、溶液浓度和温度的变化,并采用具有界面校正的粘度方程从实验相对粘度数据计算明胶在聚氨酯表面的吸附量。研究发现明胶分...     

钒酸铋黄色颜料的制备——推荐一个无机化学教学实验

该实验以Bi(NO_3)_3和NH_4VO_3为原料,采用液相沉淀法,制备钒酸铋黄色颜料。学生通过控制反应物初始浓度、溶液pH、温度与时间等条件制备分散性良好、颗粒细小、组成均匀的钒酸铋。实验涉及溶液配制、加热搅拌、简易回流、控温、调pH、检验、抽滤、洗涤、干燥等操作。钒酸铋是一种绿色环保的黄色颜料,且具有降解污染物的光催化性能,因此,该实验不仅对于提高学生无机制备实验能力具有很好的教学效果,还在实验教学中渗透了环保理念。     

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.