结晶聚合物中间层理论与实验佐证

概述了Ｆｌｏｒｙ和Ｙｏｏｎ由晶格模型出发，从理论上证明了结晶聚合物中间层的存在以及近年来许多学者采用多种实验技术确认中间层存在的事实。     

Effect of tetrahydrofuran on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures

The molar conductance of dilute solutions of HCl in wet (68.5% methanol + 31.5% tetrahydrofurane mixtures at 25°C have been measured. The data were analyzed using the Fuoss-Hsia equation to calculate the infinite dilution molar conductances and association constants. The trend of the limiting conductances in these mixtures as a function of the water content shows, once more, the peculiar minimum due to the anomalous proton conductance mechanism. From these data the limiting molar conductance in the anhydrous binary solvent system was evaluated. The percentage excess proton mobility with respect to potassium ion has also been determined. All these data are compared to those found in a binary isodielectric methanol mixture containing as cosolvent 1,4-dioxane. This comparison shows that proton mobilities are very similar in both solvent mixtures. The dielectric constants, refractive indices, viscosities and densities of the methanol-tetrahydrofuran mixtures in the whole mole fraction range have been measured and are reported. An analysis of the excess molar volumes and viscosities shows a slight deviation of this system from ideality.     

Study of the first nucleation steps of thin films by XPS inelastic peak shape analysis

The initial steps in the formation of thin films have been investigated by analysis of the peak shape (both inelastic background and elastic contributions) of X‐ray photoelectron spectra. Surface coverage and averaged height of the deposited particles have been estimated for several overlayers (nanometre range) after successive deposition cycles. This study has permitted the assessment of the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of an XPS spectrometer. To check the performance of the method, several materials (i.e. cerium oxide, vanadium oxide and cadmium sulfide) have been deposited on different substrates using a variety of preparation procedures (i.e. thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition). It is shown that the first deposited nuclei of the films are usually formed by three‐dimensional particles whose heights and degree of surface coverage depend on the chemical characteristics of the growing thin film and substrate materials, as well as the deposition procedure. It is concluded that XPS peak shape analysis can be satisfactorily used as a general method to characterize morphologically the first nanometric moieties that nucleate a thin film. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation of VPS and PVD coatings for metallographic and TEM investigations

The aim of the first part of the paper is to give some advice for the faultless metallographic preparation of vacuum plasma sprayed coatings. Several coating/substrate combinations using metals, alloys and ceramics were investigated to derive some general rules. The second part deals with a preparation technique for cross-sections- of physical vapour deposition coatings. This technique was optimized for TiN and Ti(C, N) coatings on hardmetals which were examined in an analytical transmission electron microscope.     

物理化学课程“热化学”主题学习历程研究——化学师范生知识建构的文本分析

为深入了解地方性师范院校化学师范生知识建构习惯和水平，探讨他们在大学专业基础课程中的学习历程，以物理化学课程中以“融合科学读写特色”的“热化学”学案作为研究载体，研究对象在学案引导下开展自学活动，并在阅读教材和文献基础上进行科学写作。采用量表工具针对大学生自学效果和反思活动进行评价，并采用SOLO分类评价科学写作作品，采用KWL工具评价学生的科学阅读收获。结果发现研究对象学习动机不强，不擅长在新的学科知识学习中联系已有专业课程知识，基于文本学习的建构活动水平极低，可能是因为他们在应试背景下的基础知识并未形成体系，先修课程中并未培养元认知学习策略。     

Identification of low molecular weight proteins isolated by 2-D liquid separations

Proteins with molecular mass (M(r)) <20 kDa are often poorly separated in 2-D sodium dodecyl sulfate polyacrylamide gel electrophoresis. In addition, low-M(r) proteins may not be readily identified using peptide mass fingerprinting (PMF) owing to the small number of peptides generated in tryptic digestion. In this work, we used a 2-D liquid separation method based on chromatofocusing and non-porous silica reversed-phase high-performance liquid chromatography to purify proteins for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis and protein identification. Several proteins were identified using the PMF method where the result was supported using an accurate M(r) value obtained from electrospray ionization TOFMS. However, many proteins were not identified owing to an insufficient number of peptides observed in the MALDI-TOF experiments. The small number of peptides detected in MALDI-TOFMS can result from internal fragmentation, the few arginines in its sequence and incomplete tryptic digestion. MALDI-QTOFMS/MS can be used to identify many of these proteins. The accurate experimental M(r) and pI confirm identification and aid in identifying post-translational modifications such as truncations and acetylations. In some cases, high-quality MS/MS data obtained from the MALDI-QTOF spectrometer overcome preferential cleavages and result in protein identification.     

A comparison of electron ionization mass spectra obtained at 70 eV,low electron energies,and with cold EI and their NIST library identification probabilities

Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that

1. Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
2. Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
3. Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
4. Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.

These conclusions are demonstrated and supported by experimental data in nine figures and two tables.     

Application of diode array detectors for solute identification in toxicological analysis

Summary The possibilities and limitation of automated solute identification via UV/VIS spectroscopy in HPLC are demonstrated and applications in toxicologic analysis are described. A standard isocratic system is used. The influence of various chromatographic parameters on retention time is shown. A retention time window of ±15% is required. In addition to retention time, derived spectral data are calculated (minima and maxima of derivatives, area counts under standardized spectral ranges, absorption at various wavelength) and used for positive solute identification. It is possible to identify solutes with a high degree of certainty in urine and plasma if their concentration is at least 10 ppm.     

Structure-activity relationship of Ca2+ channel blockers: A study using conformational analysis and chemometric methods

Summary A structure-activity relationship study has been done on 8 compounds with the activity known as Ca²⁺ channel blockers. Conformational analysis was carried out using a molecular mechanics method. The 3D-QSAR approach was used and the most polar functional groups present in all the molecules were considered. Eight interatomic distances are necessary to define the relative spatial disposition of these relevant molecular fragments. The structure-activity relationship between interatomic distances and biological activity was performed using statistic and chemometric methods. In particular, with Principal Component Analysis, it was possible to reduce the number of interatomic distances: only six of the eight distances are sufficient to describe the system in a useful way. A classification method was iteratively used to select the most probable conformations linked to the biological activity and to build a model able to classify conformations according to their biological behaviour. Cluster analysis on the active selected conformations subsequently allowed the identification of two different geometrical patterns for the active compounds. Finally the validity of the model was verified by correctly predicting the activity of other molecules not used in the construction of the model but possessing known activity.