关于物理化学实验教学改革的几点思考

探讨物理化学实验的目的、内容、要求及成绩评定方法,提出用演示实验改造物理化学实验。     

物理化学理论体系中的几种基本研究方法

理想模型化法、标准状态法、可逆过程极值法和微元法是物理化学中具有典型学科特征的基本理论研究方法,在物理化学理论体系的形成和发展过程中相应形成并贯穿整个学科。本文从科学方法论的角度,归纳总结了四种理论研究方法的研究目的、处理方法及相应规定和结论,并对它们在物理化学理论体系中的具体应用通过实例予以分析和说明。同时阐述了如果掌握并深刻领会了这些科学研究方法,将有助于学习者构建物理化学宏观知识体系,培养逻辑思维能力,增强分析问题和解决问题能力。     

物理化学中的热力学方法、拓展及应用

主要依托物理化学中的热力学基本原理,浅议热力学方法、简介化工热力学方法和工程热力学方法及应用等。热力学方法主要有循环法、特性函数法、变量变换法、标准状态法、平衡法及极值法、微元法等,并归纳了各种方法的特点、作用及意义。对于学生学习物理化学中的热力学,具有一定的指导意义,拓展了热力学的基本知识。     

浅议物理化学课程的教学实践与改革

物理化学是化学及相关专业学生的必修课,在当前形势下进行物理化学课程教学内容与方法的改进显得尤为必要。本文主要从教学内容,实验环节,学生创新能力与素质提高等方面进行了讨论。     

物理化学理论与实验教学内容更新与教学模式改革——物理化学教学研究会第五次会议纪要

物理化学教学研究会第五次会议以物理化学及物理化学实验"金课"建设的思路与举措为主题,围绕物理化学教学内容更新、物理化学课程思政建设和学科思维教育、物理化学实验创新设计三个方面展开研讨。相关讨论对今后物理化学课程和实验教学内容更新和教学模式改革具有一定的指导意义。     

2002年全国冶金物理化学学术会议征文启事(第一轮)

20 0 2年全国冶金物理化学学术会议 ,定于 2 0 0 2年 9月～ 10月在鞍山及大连两地召开。会议由中国自然科学基金委员会工程与材料学部、中国金属学会冶金物理化学专业委员会、中国有色金属学会冶金物理化学专业委员会、中国稀土学会主办 ,由鞍山钢铁学院承办 ,东北大学协办。全国冶金物理化学学术会议是我国冶金物理化学学科大型学术会议 ,每两年召开一届。征文内容 :1.冶金及材料物理化学研究现状及发展趋势 ;2 .冶金热力学 ;3.冶金动力学及反应工程学 ;4 .计算物理化学 ;5 .冶金及能源电化学 ;6.材料制备的物理化学 ;7.冶金工艺的物理化学…     

计算机与化学应用Matlab处理物理化学实验数据

提出了运用Matlab软件处理物理化学实验数据的方法。通过计算机Matlab语言编程对物理化学实验中采集的离散数据进行直线拟合,能够方便、快速地得出斜率及截距,从而获得待测定物理量。     

关于铜极和锌极组成的原电池的命名

在物理化学教学中对于Zn|ZnSO_4|CuSO_4|Cu这种电池有的教师讲为丹聂尔电池有的讲为雅可比电池,同时在几本苏联译本的物理化学书中也是不一致的。如物理化学及胶体化学上册(周念祖,李存朴译),物理化学及胶体化学下册(虞宏正等译)中皆称为丹聂尔电池。而物理化学下卷(张志炳等译)物理化学     

欢迎订阅《物理化学学报》

2012年全国报刊杂志征订工作已经开始,敬请向贵单位推荐订阅2012年《物理化学学报》.《物理化学学报》是由中国科协主管,中国化学会主办,北京大学化学与分子工程学院承办的基础学科类学术刊物.《物理化学学报》设有通讯、研究论文和综述等栏目,报导物理化学学科及交叉学科的基础研究及应     

“问题解决”策略在高等农业院校物理化学教学中的实践

"问题解决"策略方法是以学生为中心的教学模式,能激发学生的学习兴趣和主观能动性。结合高等农业院校的教学现状和物理化学课程特点,将其应用到具体的教学实践中。经过课堂过程设计、教学法实践的准备、教学实践及教学评价,说明该方法能较大提高物理化学课程的学习效果。     

Experiences with a researcher-centric ELN

Electronic Laboratory Notebooks (ELNs) are progressively replacing traditional paper books in both commercial research establishments and academic institutions. University researchers require specific features from ELNs, given the need to promote cross-institutional collaborative working, to enable the sharing of procedures and results, and to facilitate publication. The LabTrove ELN, which we use as our exemplar, was designed to be researcher-centric (i.e., not only aimed at the individual researcher''s basic needs rather than to a specific institutional or subject or disciplinary agenda, but also able to be tailored because it is open source). LabTrove is being used in a heterogeneous set of academic laboratories, for a range of purposes, including analytical chemistry, X-ray studies, drug discovery and a biomaterials project. Researchers use the ELN for recording experiments, preserving data collected, and for project coordination. This perspective article describes the experiences of those researchers from several viewpoints, demonstrating how a web-based open source electronic notebook can meet the diverse needs of academic researchers.     

Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C₆F₅E)₂ (13a–c) and (2,6-Mes₂C₆H₃E)₂ (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF₅ and SbF₅ gave rise to the formation of thermally unstable radical cations [(C₆F₅S)₂]˙⁺ (14a) and [(C₆F₅Se)₂]˙⁺ (14b) that were isolated as [Sb₂F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of 13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.     

A hexanuclear gold carbonyl cluster

The hexanuclear gold carbonyl cluster [PPh₄]₂[Au₆(CF₃)₆Br₂(CO)₂] (4) has been obtained by spontaneous self-assembly of the following independent units: CF₃AuCO (1) and [PPh₄][Br(AuCF₃)₂] (3). The cyclo-Au₆ aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm^–1 in the separate component 1 to 2171 cm^–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh₄][CF₃AuBr] (2) are also reported.     

Conducting polyfurans by electropolymerization of oligofurans

Polyfurans have never been established as useful conjugated polymers, as previously they were considered to be inherently unstable and poorly conductive. Here, we show the preparation of stable and conducting polyfuran films by electropolymerization of a series of oligofurans of different chain lengths substituted with alkyl groups. The polyfuran films show good conductivity in the order of 1 S cm^–1, good environmental and electrochemical stabilities, very smooth morphologies (roughness 1–5 nm), long effective conjugation lengths, well-defined spectroelectrochemistry and electro-optical switching (in the Vis-NIR region), and have optical band-gaps in the range of 2.2–2.3 eV. A low oxidation potential needed for polymerization of oligofurans (compared to furan) is a key factor in achievement of improved properties of polyfurans reported in this work. DFT calculations and experiments show that polyfurans are much more rigid than polythiophenes, and alkyl substitution does not disturb backbone planarity and conjugation. The obtained properties of polyfuran films are similar or superior to the properties of electrochemically prepared poly(oligothiophene)s under similar conditions.     

Expanding discriminative dimensions for analysis and imaging

Eliminating the contribution of interfering compounds is a key step in chemical analysis. In complex media, one possible approach is to perform a preliminary separation. However purification is often demanding, long, and costly; it may also considerably alter the properties of interacting components of the mixture (e.g. in a living cell). Hence there is a strong interest for developing separation-free non-invasive analytical protocols. Using photoswitchable probes as labelling and titration contrast agents, we demonstrate that the association of a modulated monochromatic light excitation with a kinetic filtering of the overall observable is much more attractive than constant excitation to read-out the contribution from a target probe under adverse conditions. An extensive theoretical framework enabled us to optimize the out-of-phase concentration first-order response of a photoswitchable probe to modulated illumination by appropriately matching the average light intensity and the radial frequency of the light modulation to the probe dynamics. Thus, we can selectively and quantitatively extract from an overall signal the contribution from a target photoswitchable probe within a mixture of species, photoswitchable or not. This simple titration strategy is more specifically developed in the context of fluorescence imaging, which offers promising perspectives.     

Biosynthetic insights provided by unusual sesterterpenes from the medicinal herb Aletris farinosa

A series of novel sesterterpenes (2–6) have been isolated from the roots of Aletris farinosa and structurally characterized by MS, NMR, and X-ray crystallography in conjunction with computational modeling. Their structures provide new insights into the mechanisms of sesterterpene biosynthesis. Specifically, we propose with support from density functional theory computations that the configuration at a single stereocenter determines the fate of a key tetracyclic carbocationic intermediate, derived from an oxidogeranylfarnesol precursor. Whereas one epimer of the carbocation undergoes H⁺ elimination to give 6, the other undergoes a spectacular cascade of seven 1,2-methyl and hydride migrations leading to the previously unreported carbon skeleton of 5. Theoretical calculations suggest that the cascade is triggered by substrate preorganization in the enzyme active site.     

Azasugar inhibitors as pharmacological chaperones for Krabbe disease

Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease.     

Boronic acids facilitate rapid oxime condensations at neutral pH

We report here the discovery and development of boron-assisted oxime formation as a powerful connective reaction for chemical biology. Oximes proximal to boronic acids form in neutral aqueous buffer with rate constants of more than 10⁴ M^–1 s^–1, the largest to date for any oxime condensation. Boron''s dynamic coordination chemistry confers an adaptability that seems to aid a number of elementary steps in the oxime condensation. In addition to applications in bioconjugation, the emerging importance of boronic acids in chemical biology as carbohydrate receptors or peroxide probes, and the growing list of drugs and drug candidates containing boronic acids suggest many potential applications.     

A macrocycle-assisted nanoparticlization process for bulk Ag2S

We report herein a new nanoparticlization process for the bulk-to-nano transformation of Ag₂S by incorporating both top-down and bottom-up approaches. Bulk Ag₂S was dissolved in solution with the assistance of a macrocyclic ligand, hexamethylazacalix[6]pyridine (Py[6]), to produce polynuclear silver sulfide cluster aggregates. All Ag–S cluster aggregates obtained in three crystalline complexes were protected by Py[6] macrocycles. Removing the protective Py[6] macrocycles by protonation led to the generation of unconventional Ag–S nanoparticles with a large energy gap. Theoretical calculations by a hybrid DFT method demonstrated that the silver sulfide clusters with high Ag/S ratio exhibited more localized HOMO–LUMO orbitals, which consequently enlarged their band gap energies. These experimental and theoretical studies broaden our understanding of the fabrication of nanomaterials by virtue of the advantages of both bottom-up and top-down methods and meanwhile provide a viable means of adjusting the band gap of binary nanomaterials independent of their size.     

Solid–Liquid Phase Equilibria in the Ternary Systems (LiBO 2 + NaBO 2 + H 2 O) and (LiBO 2 + KBO 2 + H 2 O) at 288.15 K and 0.1 MPa

Solid–liquid phase equilibria for the two aqueous systems (LiBO2 + NaBO2 + H2O) and (LiBO2 + KBO2 + H2O) at T = 288.15 K and p = 0.1 MPa were determined using the isothermal dissolution equilibrium method. The experimental results show that the phase diagrams consist of one two-salt co-saturated invariant point, two univariant solubility isotherms, and three crystallization fields. The two systems belong to simple co-saturated type, and neither double salt nor solid solution were found. The densities change regularly as the sodium metaborate (potassium metaborate) concentration increases in solution, and reach their maximum values at the invariant point. Based on the Pitzer and its extended Harvie–Møller–Weare (HMW) model, the solubilities for the ternary systems at 288.15 K were represented, and the calculated results agree well with the experimental values.