Metallacarboranes of the C2B4-cage systems

A comprehensive review of the chemistry of polyhedral cluster complexes in whichs,p,d, andf-block metals are incorporated into C₂B₄-carborane cages to form the respective metallacarboranes is presented. The main focus of the review is directed toward systematizing the chemistry of metallacarboranes in order to promote their use as possible electronic, ceramic, and/or catalytic materials in addition to providing information on which we can test and expand our knowledge about the fundamental interactions that are at work in determining the structures and properties of these cluster complexes.     

从化学学科核心素养到学生学习活动*——基于证据推理与模型认知的“空气”教学

以学生活动为载体,借助表现性评价,有助于学生学科核心素养的形成。根据“表现性评价”和“证据推理与模型认知”的内涵,从“获取推理证据”“基于证据推理”“建立认知模型” “基于模型认知”等4个维度提出表现性评价量规,以 “空气”第1课时教学内容为例,设计表现性任务。介绍了在“空气”第1课时的教学中,教师在课堂上基于表现性评价观测学生课堂表现,并根据学生素养达成情况及时调整教学,展开“教、学、评”一体化的教学过程。     

改性三聚氰胺泡塑富集-电感耦合等离子体质谱(ICP-MS)法测定矿样中的钯

钯的富集常用泡塑作为载体，而通常对泡塑的处理过程需要使用带有胺基的有机试剂，以确保泡塑的官能团带有正电荷，用于富集带有负电荷的钯络阴离子。本文选用10%(V/V)盐酸对三聚氰胺进行处理，该方法泡塑处理过程简单易实现，且对环境友好。样品用HCl-H2O2体系进行消解，避免了NO3-的引入。在盐酸浓度低于10%（V/V），振荡时间为80min时，选择高温灰化法，Pd的回收率可达到 95%以上。以铂族元素国家一级标准物质进行验证，测定值与认定值基本一致。相对标准偏差（RSD）Pd为3.73%~6.76%。可以满足大部分矿样中Pd的分析检测。     

ChemInform Abstract: A Structural Investigation of the Singly Layered Silicates,Silinaite and Makatite,by Vibrational Spectroscopy.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

ChemInform Abstract: IR Spectra of As4-Ozone Reaction and Photolysis Products in Solid Argon.

The codeposition of As4 and O3 with excess argon at 14-17 K produces new IR bands at 921.7, 590.3 and 565.4 cm^-1, whose intensities are increased by red-light photolysis.     

Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh₃)₂Pt(P^tBu)₃], [(PPh₃)₂Pd(P^tBu)₂], [(CO)₄Cr{(PⁱPr)₃}₂], [RhCl(PPh₃)(P^tBu)₃], [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂], and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh₃)₂Pt(P^tBu)₃] ( 1 ), [(PPh₃)₂Pd(P^tBu)₂] ( 2 ), [(CO)₄Cr{(PⁱPr)₃}₂] ( 3 ), [RhCl(PPh₃)(P^tBu)₃] ( 4 ), [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂] ( 5 ) and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P2₁/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P2₁/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P2₁/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).     

Cluster models in the quantum-chemical analysis of coordination of nitroxide probes to Lewis acid sites on the surface of Al2O3

The results of ESR-spectroscopic and quantum-chemical investigations of the coordination of 2,2,6,6-tetramethylpiperidineN-oxyl, 2,2,3,4,5,5-hexamethyl-3-imidazolidineN-oxyl, 2,2,4,5,5-pentamethyl-3-imidazolineN-oxyl, 2,4,5,5-tetramethyl-2-phenyl-3-imidazolineN-oxyl, and 2,4,5,5-tetramethyl-2-octyl-3-imidazolineN-oxyl to Lewis acid sites (LAS) on alumina surface are described systematically and analyzed. The cluster models of LAS accepted in radiospectroscopy and based on experimental data on g-factors and hyperfine coupling constants with N and Al nuclei in the corresponding donor-acceptor complexes are discussed. Within the framework of the unrestricted Hartree—Fock (UHF) method using the STO-3G, STO-6G, 3–21G, and 6–31G basis sets and also in terms of semiempirical MNDO, AM1, and PM3 procedures, comparative quantum-chemical analysis of the structural, spin, electrostatic, energy, and radiospectroscopic characteristics of the coordination of the model cluster LAS to the simplest representative of nitroxides is performed. Three illustrative types of structures of the resulting surface complex are considered. A semiquantitative interpretation of the whole set of features found experimentally for the coordination of nitroxide probes to the surface LAS on alumina is given. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1743–1756, October, 1997.     

阿基瑞林制备方法的改进研究

阿基瑞林,又称乙酰基六肽-8、六胜肽等。它作为肉毒毒素的安全替代品,具有显著的抗皱活性,是美妆市场上需求潜力很大的抗皱多肽原料。当前阿基瑞林主要是通过固相合成方法得到的,由于所使用的Rink Amide AM树脂单价高、上载量低,造成了阿基瑞林原料价格高昂,不利于其大规模生产及推广应用。本文中使用固-液相结合的方法,首先用高上载量、单价低的2-CTC树脂合成六肽片段,六肽片段再经酰胺化处理得阿基瑞林粗品,粗品经纯化后得纯度95%以上的阿基瑞林,收率59.77%。本方法成本低、收率高,为C端酰胺化多肽的合成提供了一种新思路。     

Coulombic and ring-shaped potentials treated in a unified way via a nonbijective canonical transformation

This paper is concerned with the three-dimensional potentialV _q =² (2a ₀/r–q a ₀ ²/r ² sin² ) ₀ which comprises as particular cases the ring-shaped potential (q = 1) and the Coulomb potential (q = 0). The Schrödinger equation for the potentialV _q is transformed via a nonbijective canonical transformation, viz., the Kustaanheimo-Stiefel transformation, into a coupled pair of Schrödinger equations for two-dimensional harmonic oscillators with inverse-square potentials. As a consequence, the discrete spectrum for the potentialV _q is obtained in a straightforward way. A special attention is paid to the caseq = 0. In particular, the coupled pair of Schrödinger equations for two-dimensional harmonic oscillators is tackled in the situations where the spectrum for the potentialV ₀ is discrete, continuous, or reduced to the zero point. Finally, some group-theoretical questions about the potentialV _q are mentioned as well as a connection, via the Kustaanheimo-Stiefel and the Levi-Civita transformations, between the quantum-mechanical problems for the potentialV _q and the Sommerfeld and Kratzer potentials.     

Chain fragmentation under liquid-state and solid-state conditions

Thermally Activated fragmentation of copolycarbonates PC(T_xA_1-x) of bisphenol A (unit CA) and the Heat-sensitive diol 1,1,2,2-tetraethyl-1,2-di-(p-hydroxy) phenylethane (unit CT) was studied in the bulk, i.e., in the pure copolymers and in their blends with the polycarbonates of bisphenol A (PCA) or tetramethyl bisphenol A (TMPC). Fragmentation proceeds via dissociation followed by disproportionation at the central C? C bond of the unit CT. The reaction has rates that are convenient to study near the glass transition temperature. The “chemical” time constants τ for the entire reaction and τ₂ for the disproportionation step compete with the “physical” time constants δ_α for segmental motion and δ_q for fragment diffusion. A cage effect is observed below τ₂ = δ_α and effects of delayed matrix response below τ = δ_α and τ = δ_q. Owing to the two latter effects, parameters such as the glass transition temperature and the structure factor of concentration fluctuations do not respond primarily to the fragmentation, but rather to subsequent relaxation and diffusion processes in the polymer matrix.     

化学专业概论教学中的课程思政探索与实践*——以华中科技大学“一院一品”化学专业概论课为例

课程思政是高校落实立德树人根本任务的重要举措,是完善“三全育人”的重要抓手。化学是我国科学研究的重要基础,对提升原始创新能力具有重要意义。化学专业教学中融入思想政治教育的前提是建设好一门课程。针对当前专业课教学中存在的课程思政体系不完善、思政元素与专业课程融合程度低、教师思政教学水平有待提高等问题,以华中科技大学化学与化工学院专业概论课为试点,完善课程设计与教学方法,探索化学专业教学中的课程思政建设。通过剖析化学课程思政的意义与难点,构建专业概论课实施方案,形成一套行之有效的化学课程思政建设体系。     

ChemInform Abstract: Identification of Diborane(4) with Bridging B—H—B Bonds.

Photolysis of B₂H₆ dispersed in solid neon with far‐UV light (120—220 nm) at 3 K leads to the formation of B₂H₄, which is characterized by IR spectroscopy and B3LYP quantum chemical computations.     

L-半胱氨酸和胱胺共自组装膜活体检测抗坏血酸

自组装单分子膜（SAM）由于其独特的物理化学性质近年来受到了极大的关注. SAM通过金硫键在电极表面形成高度有序的单分子膜,该稳定的分子膜不仅可以调节表面的亲疏水性质,而且可以促进电极表面氧化还原活性分子的反应速率. 本论文提出了一种简单有效的方法,在金微电极上构建半胱氨酸和胱胺共自组装单分子膜用于活体内抗坏血酸的检测. 研究发现,当混合单分子层中半胱氨酸和胱胺的摩尔比为1:1时,可以在低电位下（约为0.10 V）显著增强抗坏血酸氧化的电子转移动力学,同时该膜能在一定程度上抵抗蛋白质在电极表面的非特异性吸附. 将共自组装单分子膜应用到活体检测中,作者检测到鼠纹状体中抗坏血酸的基准值为257±30mmol·L^-1（n = 3）. 本论文为活体电化学检测提供了一种简单、有效的方法.     

Modulation of Supramolecular Interactions of Urea-based Supramolecular Polymers via Molecular Structures

Linear bis-urea D230 series and branched tris-urea T403 series of supramolecular monomers were synthesized using low molecular weight polyetheramine D230, T403 and isocyanates with diverse functional groups. Rheological tests reveal that the materials possess special thermal and mechanical properties due to the strong hydrogen bonding interactions between terminal urea groups and the high flexibility of the polyetheramine middle segments. By enhancing the hydrogen bonding interactions through electronic effects of the substituted urea groups, the mechanical properties of the bulk material can be increased. Moreover, the branched T403 series with higher hydrogen bonding density also shows better performance against D230 series with the same substituted urea groups. The presence of π-π stacking between the phenyl groups in samples with phenylurea residues, which complements the hydrogen bonding, was also confirmed by fluorescence spectroscopy, therefore resulting in a stronger supramolecular polymer network.     

Mechanisms of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes

The mechanism of synthesis of maleic and succinic anhydrides from acetylene and CO in the PdBr₂−LiBr-organic solvent catalytic system was studied using the procedure of advancement and discrimination of hypotheses. The hypotheses were obtained using the data bank on elementary steps and the Combl combinatorial program. The discrimination of the hypotheses was based on the data of NMR and IR spectroscopy, studies of isotope exchange, the role of potential organic intermediates, the kinetic isotope effect, and one-factor kinetic experiments. The most probable mechanism of synthesis of maleic anhydride includes insertion of acetylene and CO into the Pd−Pd bond of the Pd^I complex, which is formed from Pd^II at the initial step of the process. Succinic anhydride results from the intramolecular transformation of the hydride complex of palladium and maleic anhydride. The palladium hydride complexes detected in the contact solution apparently play the crucial role in the conjugation of oxidation, reduction, and addition type reactions. Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1104–1115, June, 1998.     

ChemInform Abstract: Matrix Reactions of SiH4 and GeH4 with F2. IR Spectra of Several HF Product Complexes.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Synthesis of α-Oxoketene CyclicO,S and S,S Acetals

Ｓｙｎｔｈｅｓｉｓｏｆα－ＯｘｏｋｅｔｅｎｅＣｙｃｌｉｃＯ,ＳａｎｄＳ,ＳＡｃｅｔａｌｓＬＩＵＱｕｎ,ＸＵＢａｉ－ｌｉｎｇａｎｄＺＨＡＯＨｏｎｇ－ｗｕ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ,ＮｏｒｔｈｅａｓｔＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ,Ｃ...     

南北五味子荧光光谱差异的原因

建立了用荧光法快速鉴别五味子和部分含五味子制剂中五味子是属于北五味子还是南五味子的方法,探明了南北五味子荧光光谱差异的主要原因。研究了五味子的五种活性成分五味子醇甲、五味子酯甲、五味子甲素、五味子乙素和安五脂素的荧光性质和五味子以及护肝片乙醇提取液的荧光光谱,并用高效液相色谱测定了供试品五种活性成分的含量。研究表明：发光效率按安五脂素、五味子乙素、五味子甲素和五味子醇甲依次减弱,五味子酯甲不具有荧光性;北五味子的主要荧光物质为五味子乙素,而南五味子的主要荧光物质是安五脂素,它们是导致南北五味子荧光光谱差异的主要原因。用荧光法鉴别南北五味子具有简单、快速和灵敏的特点     

Investigation of Structures and Stabilities of AlmPn and AlmP(m+n=2～6)Clusters by DFT

The geometries,electronic states and energies of Alm Pn （ m + n = 2 ～ 6）neutral and anionic clusters have been investigated using the density functional theory（DFT）method of Becke’s three-parameter hybrid exchange functional with the nonlocal correlation of B3LYP. Structural optimization and frequency analyses are performed with the basis of 6-311G（ d）. The calculations predict the existence of a number of previously unknown isomers（i. e. ,Al3P_ and AlmPn （ m + n.5））. The calculations have also predicted that small AlP and（AlP）2 clusters adopt two-and three-dimensional structures characteristic of Si2 and Si4 clusters,while the structures of the larger AlP clusters are different completely from those of Sin clusters with the same electrons. The results show that the structures with the singlet have higher symmetries,while those with the doublet have lower symmetries. The vertical detachment energy of AlmPn （ m + n = 2 ～ 6）are also discused and the adiabatic electron affinities of AlmPn（m + n = 2 ～ 6）and also discussed at the same level. The results agree satisfactorily with the anion photoelectron spectroscopy of aluminum phosphide clusters reported recently by Gomez et al.