“能源化学”本科专业建设建议

"Energy chemistry" was approved as one of the chemistry majors for undergraduate by the Ministry of Education in 2015. Based on the ideas and ways of emerging engineering education, this paper hereby proposed some of constructive suggestions on the training objectives, graduation requirements, curriculum system, teaching contents, teaching staff and conditions for development of "energy chemistry" major.     

对“红铝”译名的异见

Red-Al是一种非常重要的铝基还原剂。国内学术界望文生义地将其直译为"红铝"是明显错误的。本文建议将其中文译名改为"还原铝"。     

Switching "on" and "off" the expression of chirality in peptide rotaxanes

The hydrogen-bond-directed synthesis, X-ray crystal structures, and optical properties of the first chiral peptide rotaxanes are reported. Collectively these systems provide the first examples of single molecular species where the expression of chirality in the form of a circular dichroism (CD) response can selectively be switched "on" or "off", and its magnitude altered, through controlling the interactions between mechanically interlocked submolecular components. The switching is achievable both thermally and through changes in the nature of the environment. Peptido[2]rotaxanes consisting of an intrinsically achiral benzylic amide macrocycle locked onto various chiral dipeptide (Gly-L-Ala, Gly-L-Leu, Gly-L-Met, Gly-L-Phe, and Gly-L-Pro) threads exhibit strong (10-20k deg cm(2) dmol(-1)) negative induced CD (theta;) values in nonpolar solvents (e.g. CHCl(3)), where the intramolecular hydrogen bonding between thread and macrocycle is maximized. In polar solvents (e.g., MeOH), where the intercomponent hydrogen bonding is weakened, or switched off completely, the elliptical polarization falls close to zero in some cases and can even be switched to large positive values in others. Importantly, the mechanism of generating the switchable CD response in the chiral peptide rotaxanes is also determined: a combination of semiempirical calculations and geometrical modeling using the continuous chirality measure (CCM) shows that the chirality is transmitted from the amino acid asymmetric center on the thread via the macrocycle to the C-terminal stopper of the rotaxane. This understanding could have important implications for other areas where chiral transmission from one chemical entity to another underpins a physical or chemical response, such as the seeding of supertwisted nematic liquid crystalline phases or asymmetric synthesis.     

On the nature of organic catalysis "on water"

A molecular origin of the striking rate increase observed in a reaction on water is studied theoretically. A key aspect of the on-water rate phenomenon is the chemistry between water and reactants that occurs at an oil-water phase boundary. In particular, the structure of water at the oil-water interface of an oil emulsion, in which approximately one in every four interfacial water molecules has a free ("dangling") OH group that protrudes into the organic phase, plays a key role in catalyzing reactions via the formation of hydrogen bonds. Catalysis is expected when these OH's form stronger hydrogen bonds with the transition state than with the reactants. In experiments more than a 5 orders of magnitude enhancement in rate constant was found in a chosen reaction. The structural arrangement at the "oil-water" interface is in contrast to the structure of water molecules around a small hydrophobic solute in homogeneous solution, where the water molecules are tangentially oriented. The latter implies that a breaking of an existing hydrogen-bond network in homogeneous solution is needed in order to permit a catalytic effect of hydrogen bonds, but not for the on-water reaction. Thereby, the reaction in homogeneous aqueous solution is intrinsically slower than the surface reaction, as observed experimentally. The proposed mechanism of rate acceleration is discussed in light of other on-water reactions that showed smaller accelerations in rates. To interpret the results in different media, a method is given for comparing the rate constants of different rate processes, homogeneous, neat and on-water, all of which have different units, by introducing models that reduce them to the same units. The observed deuterium kinetic isotope effect is discussed briefly, and some experiments are suggested that can test the present interpretation and increase our understanding of the on-water catalysis.     

Probing the donor-acceptor proximity on the physicochemical properties of porphyrin-fullerene dyads: "tail-on" and "tail-off" binding approach.

A new approach of probing proximity effects in porphyrin-fullerene dyads by using an axial ligand coordination controlled "tail-on" and "tail-off" binding mechanism is reported. In the newly synthesized porphyrin-fullerene dyads for this purpose, the donor-acceptor proximity is controlled either by temperature variation or by an axial ligand replacement method. In o-dichlorobenzene, 0.1 M (TBA)ClO(4), the synthesized zincporphyrin-fullerene dyads exhibit seven one-electron reversible redox reactions within the accessible potential window of the solvent and the measured electrochemical redox potentials and UV-visible absorption spectra reveal little or no ground-state interactions between the C(60) spheroid and porphyrin pi-system. The proximity effects on the photoinduced charge separation and charge recombination are probed by both steady-state and time-resolved fluorescence techniques. It is observed that in the "tail-off" form the charge-separation efficiency changes to some extent in comparison with the results obtained for the "tail-on" form, suggesting the presence of some through-space interactions between the singlet excited zinc porphyrin and the C(60) moiety in the "tail-off" form. The charge separation rates and efficiencies are evaluated from the fluorescence lifetime studies. The charge separation via the singlet excited states of zinc porphyrin in the studied dyads is also confirmed by the quick rise-decay of the anion radical of the C(60) moiety within 20 ns. Furthermore, a long-lived ion pair with lifetime of about 1000 ns is also observed in the investigated zinc porphyrin-C(60) dyads.     

利用《CA on CD》光盘数据库查找信息资源

1　《ＣＡｏｎＣＤ》光盘数据库简介　　《ＣＡｏｎＣＤ》光盘数据库由美国化学会制作 ,文摘内容与书本式《化学文摘》相对应 ,收录了世界范围内有关化学及化工方面的大量科技文献 ,年文献量达 77.3万条 ,其中约 1 2 .3万条专利。数据库文献内容及索引信息按月更新。2　《ＣＡｏｎＣＤ》的检索方法　　《ＣＡｏｎＣＤ》提供下面 4种基本检索途径 :　　 ( 1 )词条检索 (ＷｏｒｄＳｅａｒｃｈ)　　在检索菜单窗口 ,点击Ｓｅａｒｃｈ键或在Ｓｅａｒｃｈ命令菜单中选择ＷｏｒｄＳｅａｒｃｈ命令 ,在检索词对话框中输入检索词 ,用鼠标点击Ｓｅａ…     

Three-component coupling based on the "cation pool" method

Sequential one-pot three-component coupling reactions have been developed based on the "cation pool" method. An N-acyliminium ion generated by the "cation pool" method adds to an electron-rich carbon-carbon double bond, such as enamine derivatives and vinyl sulfides, to form the second "cation pool". The addition of nucleophiles such as allylsilanes, enol silyl ethers, Grignard reagents, and organoaluminum compounds led to the formation of the corresponding three-component coupling products.     

也谈《高分子化学》课程教学的工科特色

《高分子化学》课程是大部分工科化工、材料类专业的必修课程,如何在工科专业高分子化学课程教学中体现工科特色,成为大家关注的热点.针对什么是工科特色,提出了本人的见解.并就如何在教学过程中体现工科特色介绍了本人的探索与尝试.     

"物质的量"认知结构形成的实验研究

本文从“物质的量”的教学出发，分析了物质的量教学中存在的问题。既而在定向结构教学理论的指导下对“物质的量”的教学进行了实验改革，并对教学成效进行了一定的考核与评估，最后对此次实验改革提出展望。     

Computational analysis on the dual reactivity of conjugated "ene-ene-yne" systems

The design of new reactions that yield benzo-fused five- or six-membered rings arising from conjugated ene-ene-yne precursors was examined computationally. Inclusion of heteroatoms (particularly N) in the bond making position was shown to lower activation energies due to participation of the lone pair electrons in the cyclization reactions. By systematically varying the atomic configuration in the ene-ene-yne system, the influence of heteroatoms was used to identify optimal candidates for future experimental study.     

精品课程教材《高分子物理实验》建设的体会——三个及时融入

中国科学技术大学"高分子物理实验"课程是2006年安徽省精品课程,作者结合教学研究和精品课程建设经验,总结出了"三个及时融入"的教材建设理念,本文结合实例对该理念的具体含义进行了阐述.     

"Supramolecular" assembly of gold nanorods end-terminated with polymer "pom-poms": effect of pom-pom structure on the association modes

We report a predefined self-organization of gold nanorods (NRs) end-terminated with multiple polymer arms ("pom-poms") in higher-order structures. The assembly of polymer-tethered NRs was controlled by changing the structure of the polymer pom-poms. We show that the variation in the molecular weight of the polymer molecules and their relative location with respect to the long side of the NRs resulted in two competing association modes of the nanorods, that is, their side-by-side and end-to-end assembly, and produced bundles, chains, rings, and bundled chains of the NRs. The superposition of the two variables controlling the organization of NRs allowed us to create a map showing the variation in the longitudinal plasmonic bands of the NRs achieved by their self-assembly.     

关于化学课程中"能力培养"问题的思考

本文依据20世纪70年代以来国家统一颁布的化学教学大纲为线索,从课程发展的角度对我国中学化学课程中能力培养的问题进行了探讨。文章重点考察了以下3个问题：教学大纲中关于能力的提法、能力要素的确定、能力培养和科学探究的联系与区别。     

全媒体时代仪器分析实验课程的教学改革研究

随着现代信息技术的迅猛发展,声音、图像、视频等多种媒体在课程教学中广为应用,学生在任何时间、任何地点利用信息终端完成线上自主学习成为常态,课程教学的信息全媒体时代随之而来,全媒体对实验教学带来全新要求。本文在总结近年来仪器分析实验全媒体教学经验的基础上,开展全媒体时代背景下仪器分析实验的实践教学设计、资源库建设、新型教学模式构建、课堂教学考评、教学团队建设的研究,以期提高学生自主综合学习能力和高阶思维能力,提升仪器分析实验课程的教学效果,为深入开展全媒体教学改革提供参考。