对《交流电作用下的电解过程探究》的商榷

通过实验探究交流电作用下电解氯化钠、氯化铵、氯化铁溶液,发现在一定条件下可以产生氯气,并从理论上简要分析交流电电解时电极的过程表现,对“交流电电解以电能转化为热能为主,交流电作用下OH-比Cl-容易放电”等结论提出不同看法。     

铬酸根离子的SERS检测及磁分离研究

介绍了一种基于表面增强拉曼光谱技术(SERS)的简单快速检测低浓度铬酸根离子的方法. 通过介质中水与铬酸根离子以及修饰在金基底和金纳米粒子表面的羧酸根形成氢键而构建“巯基苯甲酸-金基底/铬酸根-水/巯基苯甲酸-金纳米粒子”三明治结构. 通过检测标记分子的SERS信号判断溶液中是否存在铬酸根离子. 研究表明标记分子的SERS强度与铬酸根离子的浓度有关, 随浓度增加SERS强度呈非线性增强, 在10^－9 mol/L出现转折点. 利用以上三明治结构, 通过引入功能化的Fe₂O₃@Au核壳磁性纳米粒子, 利用外加磁场可富集分离溶液中的铬酸根离子, 经SERS 检测表明10^－5 mol/L的铬酸根离子磁分离后其浓度降低了约4～6个数量级.     

“电解池”新授课的项目式教学实践与探索*

以“纽扣镀铜”为项目学习主题,以功能导向的电解原理、电镀装置、电镀影响因素、产品评价等为项目学习活动内容,呈现“以项目式学习方式开展电解池新授课”的教学设计思路和教学实践过程。     

日本初中理科教科书中“粒子的存在”内容选择及启示

日本理科课程中“粒子”科学概念主要与化学课程相关,“粒子的存在”是“粒子”的首要核心概念,主要发展学生从微观层面认识物质的性质、结构及2者之间关系的能力,明确物质是由粒子构成的,粒子包括分子、原子和离子等,且粒子的性质决定物质的性质。从“重要事实”“核心内容”和“主要观念”3个方面自下而上对日本《新科学》教科书中“粒子的存在”相关内容的选择进行分析,发现《新科学》教科书在内容选择上具有注重“粒子模型”构建的层次性和观念层面要求显性化的特征。     

妙解盐水——高中创意电解实验设计

针对化学课堂氯碱工业电解演示实验的不足,以身边的粉笔、化妆棉等材料作载体吸收食盐水,以铁钉、铝箔、铅笔芯作电极,设计了系列反应快速、现象明显、污染极小的微型电解实验,并探讨了相关原理。创新性地将6B铅笔涂画于试纸上制成“隐形”电极,通过纸上电解绘出漂亮“化学”猫。通过食盐水电解巧制矿泉水瓶消毒液发生器,6 V电压下电解40 min后碘量法测得消毒液有效氯含量为722 mg/L,符合家庭和医院消毒标准。     

《电镀与表面精饰》专辑序言

电镀与表面精饰属于工业电化学范畴,它是一门古老的科学,有着悠久的历史,在国民经济的众多领域发挥了重要的作用. 然而,由于受到资源、环境等问题的困扰,近年来其发展受到了严格的限制. 但是,机械制造、电力电子、仪器仪表、航空航天等诸多重要行业都离不开电镀与表面精饰. 在此背景下,就迫切要求广大电镀工作者奋发图强,不懈努力,不断开发新技术、新工艺,以适应新需求,以缓解资源、环境等方面的压力. 　　电镀与表面精饰涉及的领域比较广泛,主要包括：电镀、化学镀、阳极氧化、磷化、钝化、电解加工等. 这些技术共同的发展方向是：（1）所获得的表面膜层性能更加优异,包括耐蚀性、耐磨性、导电性、可焊性、稳定性等多种性能;（2）所采用溶液的化学组成更加简单,其主要成分更加低毒、无毒,并且尽量用廉价的原材料替代稀贵材料;（3）工艺操作更加简单,维护管理更加方便;（4）尽量降低生产成本,减少电能、热能等的消耗;（5）环境更加友好,在生产过程中要尽量减少或抑制废水、废气或废渣的排放等. 　　近年来,电镀与表面精饰技术的相关研究得到了迅速发展. 除从绿色、环保等方面出发开展了三价铬电镀、无氰电镀、无铬钝化等新技术、新工艺的研究外,还开展了熔盐电沉积稀有金属及其合金、离子液体电沉积特殊功能材料等方面的研究;在研究方法方面,除采用传统的电化学测试技术和表面分析技术外,还将量化计算、分子动力学模拟方法等应用到电镀液组成优化和镀层性能预测中;电镀与表面精饰技术业已突破了传统的技术领域,其在功能材料、纳米材料制造中的应用也越来越广泛. 结合上述研究方向,本专辑刊出由国内本领域六位知名教授受邀撰写的介绍最新研究成果的相关论文. 其中包括：与电镀相关的“硫酸盐体系三价铬沉积机理及镀层表征”、“镀锡层上钛?鄄磷复合体系钝化膜的制备与表征”;与金属表面改性相关的“水热法制备铝合金超疏水表面及电化学性能研究”;与电沉积纳米材料相关的“玻碳材料脉冲电沉积纳米晶体镍的制备及其性能研究”、“激光刻蚀模板中电沉积特殊结构CIGS薄膜”;与离子液体电沉积相关的“镍离子对中磷镍基体氯化胆碱无氰浸金表面的改善”. 　　最后,对本专辑的所有作者、审稿人及编辑部工作人员的辛勤工作和付出表示由衷的感谢！     

3种铬离子的卡尔曼滤波分光光度同时测定

1 引言铬离子污染已经引起社会的重视,工业排放物中通常是6价铬离子和3价铬离子共存,6价铬随体系pH值的不同以各种形态相互转换,而pH值本身又受温度和介质等多种因素的影响,难以准确控制。这样,严重影响了分析准确性.本文利用卡尔曼滤波(简称KF),在DMS-200型分光光度计-IBM PC-AT联机系统(简称DMS-AT)的可见光谱区同时对重铬酸根、铬酸根和3价铬离子这3种不同形态的铬离子混合溶液进行了定量分析.还对半失效的重铬酸钾硫酸洗液进行了实测。由于构成KF预测模型利用了各单独组分的吸收光谱信息,因而能够直接预测在不同pH值条件下混合体系和实际样品的Cr~(3+)、Cr_2O_7~(2-)。和CrO_4~(2-)。DMS-AT系统能自动采集数据、快速计算、且操作简单,KF算法对多组分混合体系预测又有较好的准确性,可以考虑作为一种工业废水监测手段.     

高中生对化学核心概念掌握情况的测查分析——以“电解质、离子反应、化学键”概念群为例

电解质、离子反应、化学键组成一个核心概念群,是学生掌握相关知识的重难点。对北京市普通高中370名高二学生的测查显示:(1)概念掌握的程度为:化学键<离子反应<电解质。(2)“电解质的概念”与“导电原理”“离子反应概念”“离子共存”的掌握程度存在显著相关;电离与离子反应概念的掌握程度显著相关;“导电原理”与“离子反应概念”“离子共存”“离子键与共价键综合辨析”的掌握程度显著相关。表明电解质的概念、导电原理的理解与掌握是概念体系中的重要纽带。(3)优秀、中等、学困3类学生在解决容易和较难2类概念的相关问题上差异最大,而中等难度上的差异相对较小。基于此,提出了相应的核心概念教学对策。     

离子色谱-电感耦合等离子体质谱同步分离测定环境水中砷、铬、溴、碘的10种形态

建立了离子色谱-电感耦合等离子体质谱(IC-ICP-MS)联用技术，用于测定环境水中亚砷酸根、砷酸根、一甲基砷(MMA)、二甲基砷(DMA)、三价铬、铬酸根、溴离子、溴酸根离子、碘离子、碘酸根离子。使用Hamilton PRP-X100阴离子交换色谱柱，在流速1.4 mL/min、5%甲醇-40 mmol/L NH₄NO₃流动相(pH=8.6)等度洗脱条件下，20 min内实现了砷、铬、溴、碘4种元素10种形态的分离检测。10种元素形态检出限在0.1～2μg/L之间，定量限在0.5～6μg/L之间，平均加标回收率在75.4%～104.7%之间，相对标准偏差(RSD,n=3)在0.91%～4.96%之间。该方法可以用于环境水样中砷、铬、溴、碘4种元素10种形态的常规分析检测。     

光谱法研究铬(Ⅵ)与血红蛋白的相互作用

运用荧光光谱、紫外光谱、CD光谱法研究了K₂Cr₂O₇与牛血红蛋白(BHb)的相互作用。紫外光谱表明,加入铬(Ⅵ)酸根离子后,BHb分子中Soret带的吸收持续降低, 峰位红移,说明铬(Ⅵ)酸根离子可能使部分血红素辅基从BHb的空腔中脱离出来,部分转变为高铁血红蛋白。荧光光谱表明,铬(Ⅵ)酸根离子与BHb形成基态复合物导致BHb内源荧光猝灭,猝灭机理主要为静态猝灭。测定了不同温度下该反应的热力学参数,表明上述作用过程是一个熵增加、自由能降低的自发分子间作用过程,铬(Ⅵ)酸根离子与BHb之间以氢键和范徳华力相互作用为主;并用同步荧光和CD光谱技术考察了铬(Ⅵ)对BHb结构的影响。     

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.