TG-MS与Py-GC相结合法研究惰性气氛下含硫模型化合物热解过程中硫的脱除及释放行为研究

采用热重-质谱法( TG-MS)和热解-气相色谱法( Py-MS)相结合的方法对模型化合物(十四硫醇、二丁基硫醚、苯硫醚、二甲基噻吩、苯并噻吩和二苯并噻吩等)在惰性气氛下硫的脱除及释放行为进行研究。惰性气氛下硫的脱除顺序为：十四硫醇>二丁基硫醚>二甲基噻吩>苯并噻吩>苯硫醚>二苯并噻吩,苯硫醚除外,该顺序与含硫官能团的热分解顺序一致。在热解过程中,所有模型化合物在质谱和气相色谱仪上均被检测到SO2;除苯硫醚和二苯并噻吩外,其他模型化合物中均检测到了COS;而只在十四硫醇、二丁基硫醚和二甲基噻吩中检测到了H2 S。且热解气中SO2含量要显著高于H2 S和COS。这是由于活性炭作载体时,惰性气氛下内部氢的含量显著小于内部氧的含量,所以大多数的含硫自由基易与内部氧结合以SO2的形式逸出。对于苯硫醚、苯并噻吩和二苯并噻吩中没有检测到H2 S,是由于内部氢的不足,使得含硫自由基不能与内部氢结合,所以没有检测到H2 S逸出。     

TG-MS and TG-FTIR applied for an unambiguous thermal analysis of intumescent coatings

Thermogravimetry (TG), thermogravimetry coupled with mass spectroscopy (TG-MS) and thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) were used to characterise the thermo-oxidative behaviour of two intumescent coating materials. The temperature dependence, the corresponding volatile products and the amount of residue of the different processes were determined. Using both TG-MS and TG-FTIR results in an unambiguous interpretation of the volatile products. Characteristics such as the influence of endothermic reactions, the release of non-flammable gases, the dehydrogenation enhancing the char formation and the stability of the cellular char were discussed in detail. It was demonstrated, that TG, TG-MS and TG-FTIR are powerful methods to investigate mechanisms in intumescent coatings and that they are suitable methods in respect to quality assurance and unambiguous identification of such materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG-MS与Py-GC相结合法研究惰性气氛下含硫模型化合物热解过程中硫的脱除及释放行为研究

采用热重-质谱法(TG-MS)和热解-气相色谱法(Py-MS)相结合的方法对模型化合物(十四硫醇、二丁基硫醚、苯硫醚、二甲基噻吩、苯并噻吩和二苯并噻吩等)在惰性气氛下硫的脱除及释放行为进行研究。惰性气氛下硫的脱除顺序为:十四硫醇>二丁基硫醚>二甲基噻吩>苯并噻吩>苯硫醚>二苯并噻吩,苯硫醚除外,该顺序与含硫官能团的热分解顺序一致。在热解过程中,所有模型化合物在质谱和气相色谱仪上均被检测到SO₂;除苯硫醚和二苯并噻吩外,其他模型化合物中均检测到了COS;而只在十四硫醇、二丁基硫醚和二甲基噻吩中检测到了H₂S。且热解气中SO₂含量要显著高于H₂S和COS。这是由于活性炭作载体时,惰性气氛下内部氢的含量显著小于内部氧的含量,所以大多数的含硫自由基易与内部氧结合以SO₂的形式逸出。对于苯硫醚、苯并噻吩和二苯并噻吩中没有检测到H₂S,是由于内部氢的不足,使得含硫自由基不能与内部氢结合,所以没有检测到H₂S逸出。     

Loop-type interface for concurrent solvent evaporation in coupled HPLC-GC. Analysis of raspberry ketone in a raspberry sauce as an example

Presently, two coupling techniques are used for directly introducing HPLC fractions into capillary GC: The retention gap technique (involving negligible or partially concurrent solvent evaporation) and fully concurrent solvent evaporation. While the former involves use of a conventional on-column injector, it is now proposed that concurrent solvent evaporation technique be carried out using a switching valve with a built-in sample loop. The technique is based on the concept that the carrier gas pushes the HPLC eluent into the GC capillary against its own vapor pressure, generated by a column temperature slightly exceeding the solvent boiling point at the carrier gas inlet pressure. Further improvement of the technique is achieved by flow regulation of the carrier gas (accelerated solvent evaporation) and backflushing of the sample valve (improved solvent peak shape). Concurrent solvent evaporation using the loop-type interface is easy to handle, allows transfer of very large volumes of HPLC eluent (exceeding 1 ml), and renders solvent evaporation very efficient, allowing discharge of the vapors of 1 ml of solvent through the column within 5–10 min.     

Advances in host selection and interface regulation of polymer electrolytes

Polymer electrolyte (PE) has been emerging as a promising alternative to liquid electrolytes due to the unique advantages such as excellent flexibility and processability, high chemical and thermal stability, and low risk of leakage and combustion, especially for lithium-ion batteries (LIBs). Even though abundant attempts focusing on polymer chemistries have been made, the inadequate capacity of lithium-ion transport via segmental motion still cannot provide satisfying room temperature ionic conductivity and lithium-ion transference number. In addition, safety concerns and short lifespan resulted from the brittle and incompatible interface between the electrode and polymer materials also hinder the commercialization of PEs-based LIBs. Hence, for the above performance defects and interface issues, this review provides an overview of polymer electrolytes from the conductivity improvement, polymer selection and mechanical strength enhancement for protrusion suppressing. The improvement of conductivity specifically includes structure modification of poly(ethylene oxide) (PEO) host and novel electrolyte matrix beyond PEO, while the section of interface regulation mainly involves dendrite-inhibited polymers, mechanical strengthening, and in situ polymerization. Finally, perspectives and challenges are pointed out in the development of polymer electrolytes with both excellent electrochemical performance and safety for LIBs.     

Fabrication and Characterization of an Organic‐Inorganic Gradient Surface made by Polymethylsilsesquioxane (PMSQ)

Summary: A simple method for the fabrication of a chemical composition gradient from organic to inorganic by the pyrolysis of a polymethylsilsesquioxane (PMSQ) thin film in a gradient temperature field is reported. The resultant chemical gradient surface demonstrates gradual changes in wettability, and slight microstructural changes are observed along the substrate.

FT‐IR spectra of gradient PMSQ surface along the length from the unheated side to the heated side.     

An application of EGA-MS with skimmer interface to pyrolysis behavior of DHTAM, an antibacterial and antifungal material with thermostability

An application of evolved gas analysis-mass spectrometry (EGA-MS) with skimmer interface was carried out to investigate the pyrolysis mechanism of an antibacterial and antifungal material that is expected with thermostability. The skimmer interface between a furnace and a vacuum chamber with a mass spectrometer transmitted the gaseous species, which were trapped by a general capillary interface. As a result, it became clear that the thermostability of antimicrobial activity was limited by the heat resistance of the coordinate bond between nitrogen and silver in the silver chelate.     

二维液相色谱接口的改进及其在蛋白质组学研究中的应用

随着蛋白质组学、本草物质组学等组学概念的提出,所需分析的样品的成分越来越复杂,因此具有强大分离能力的多维液相色谱技术受到人们越来越多的关注。二维液相色谱中第二维的分离性能和速度是整个分离系统性能的关键。基于捕集柱模式,我们采用经特殊设计的流路系统,使得双捕集柱型接口具有预分离的功能。样品从第一维流出以后被富集在捕集柱1的柱头,经过脱盐后,正冲捕集柱,捕集柱1与第二维色谱柱联用对富集的样品进行分离,增加了第二维分离效率。当捕集柱上的样品全部被洗脱到第二维色谱柱上时,捕集柱2已经完成对第一维洗脱液中样品的捕集和脱盐,此时将阀进行切换,捕集柱2与第二维色谱柱直接相连进行洗脱。循环切换捕集柱1和捕集柱2,维持较高的阀切换频率,实现了第二维色谱柱的连续洗脱。因此保证了第二维分离具有较快速度,同时具有较高的分离效率。使用35 mm长捕集柱和十通阀为接口,以弱阴离子交换(WAX)色谱为第一维分离模式,以反相(RP)色谱为第二维分离模式,构建了WAX-RP二维液相色谱系统(2D-LC system)。以小鼠血清为样品对系统进行了初步评价。色谱流出曲线出现了明显的界面现象,这是由于捕集柱流动相中含有的较多盐分流出时的背景吸收造成的。同时,由于界面两侧的流动相黏度不同产生了黏性指进(VF)现象。当第二维色谱柱长度为50 mm时,理论上可将第二维分离效能提高70%。该接口可以应用于多种二维液相色谱模式,适用于蛋白质组学和本草物质组学研究中对于复杂样品的分离分析。     

Raman microscopic studies of the liquid-liquid interface between an organic layer and an aqueous solution containing metal ions

Raman microscopic studies of liquid-liquid interfaces between an organic layer and aqueous solutions of metal ions containing extractants are described for the first time. Using a specially constructed cell, the observation of third-phase formation which hinders the mass transfer of metals from the aqueous to the organic layers has been monitored and the spectra discussed in terms of the processes involved and the molecular interactions. The system selected for study was tri-n-butylphosphate-odourless kerosene with zirconium(IV) in aqueous nitric acid solution, a model of an industrial process for nuclear fuels reprocessing. Particulate matter at the interface between the organic and aqueous layers was identified spectroscopically as a carbonate from wash solutions used in neutralisation of the aqueous acid component.     

A comparison of ion and atom behavior in the first stage of an inductively coupled plasma mass spectrometer vacuum interface: Evidence of the effect of an ambipolar electric field

Velocities of argon atoms and calcium ions were measured in the first vacuum stage of an inductively coupled plasma mass spectrometer using high-resolution laser-excited fluorescence spectroscopy. The calcium ions reached terminal velocities in the supersonic expansion that were consistently 5–6% higher than those of argon atoms, despite minimal differences in the masses of the two species. A computational model of the expansion was developed that shows the development of an ambipolar electric field along the expansion axis. With reasonable assumptions about electron temperatures in the expansion, the model accounts for the differences between the terminal velocities of the neutral argon atoms and the singly-charged calcium ions.     

《塑料制品与模具设计》教学改革

《塑料制品与模具设计》课程是高分子材料与工程专业的一门专业课,该门课程具有多学科交叉、综合性和实践性强的特点,与实际生产生活联系紧密。本着培养应用型人才的目标,在教学过程中不断地进行教学改革探索,从理论教学和实践教学入手,注重提高学生的学习积极性和实践能力。培养学生初具模具设计能力,模具课程的改革有所成效。让模具课程改革的成果吸引更多的学生,从而更有力地推动课程的改革,更好地为培养应用型人才服务。     

Design and characterization of an engineered gp41 protein from human immunodeficiency virus-1 as a tool for drug discovery

Two new proteins of approximately 70 amino acids in length, corresponding to an unnaturally-linked N- and C-helix of the ectodomain of the gp41 protein from the human immunodeficiency virus (HIV) type 1, were designed and characterized. A designed tripeptide links the C-terminus of the C-helix with the N-terminus of the N-helix in a circular permutation so that the C-helix precedes the N-helix in sequence. In addition to the artificial peptide linkage, the C-helix is truncated at its N-terminus to expose a region of the N-helix known as the “Trp-Trp-Ile” binding pocket. Sedimentation, crystallographic, and nuclear magnetic resonance studies confirmed that the protein had the desired trimeric structure with an unoccupied binding site. Spectroscopic and centrifugation studies demonstrated that the engineered protein had ligand binding characteristics similar to previously reported constructs. Unlike previous constructs which expose additional, shallow, non-conserved, and undesired binding pockets, only the single deep and conserved Trp-Trp-Ile pocket is exposed in the proteins of this study. This engineered version of gp41 protein will be potentially useful in research programs aimed at discovery of new drugs for therapy of HIV-infection in humans.     

Sheath liquid interface for the coupling of normal-phase liquid chromatography with electrospray mass spectrometry and its application to the analysis of neoflavonoids

A novel interface that allows normal-phase liquid chromatography to be coupled with electrospray ionization (ESI) is reported. A make-up solution of 60 mM ammonium acetate in methanol, infused at a 5 microl min(-1) flow-rate at the tip of the electrospray probe, provides a sheath liquid which is poorly miscible with the chromatographic effluent, but promotes efficient ionization of the targeted analytes. Protonated molecules generated in the ESI source were subjected to tandem mass spectrometric experiments in a triple-quadrupole mass spectrometer. The main fragmentation reactions were characterized for each analyte and specific mass spectral transitions were used to acquire chromatographic data in the multiple reaction monitoring detection mode. Results obtained during optimization of the sheath liquid composition and flow-rate suggest that the electrospray process was mainly under the control of the make-up solution, and that it forms an external charged layer around a neutral chromatographic mobile phase core. This sheath liquid interface was implemented for the analysis of some neoflavonoid compounds and its performance was evaluated. Limits of detection were established for calophillolide, inophyllum B, inophyllum P and inophyllum C at 100, 25, 15 and 100 ng ml(-1), respectively.     

基于产品工程理念的聚乙二醇类物质脱硫脱氮实验教学设计*

基于产品工程理念,本着以结构-性能关系为核心,将实验教学与产品工程理念相结合的原则,对聚乙二醇类物质(PEGs)脱硫脱氮实验教学进行了设计。通过实验操作和上机数据处理等方式,逐步引导学生对PEGs的结构及其萃取性能进行量化描述,建立结构-性能之间的数学关系,并对结构进行优化设计,有利于学生正确理解“结构预测性能”和“性能优化结构”等问题,既拓展了教学内容,又使学生掌握到更多的知识和技能,符合专业的发展方向,进而达到了促进教学的目的。     

Formation of PdNiZn thin film at oil‐water interface: XPS study and application as Suzuki‐Miyaura catalyst

Nanosheet of PdNiZn and nanosphere of PdNiZn/reduced‐graphene oxide (RGO) with sub‐3 nm spheres have been successfully synthesized through a facile oil‐water interfacial strategy. The morphology and composition of the films were determined by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive analysis of X‐ray (EDAX) and elemental mapping. In the present study, we have developed a method to minimize the usage of precious Pd element. Due to the special structure and intermetallic synergies, the PdNiZn and PdNiZn/RGO nanoalloys exhibited enhanced catalytic activity and durability relative to Pd nanoparticles in Suzuki‐Miyaura C‐C cross‐coupling reaction. Compared to classical cross‐coupling reactions, this method has the advantages of a green solvent, short reaction times, low catalyst loading, high yields and reusability of the catalysts.     

工科非化学类专业物理化学的教学设计与实践

Based on the situation of China University of Petroleum (East China) and the students' training characteristics, we have explored the reasonable teaching design on the basis of combining the theory and features of physical chemistry course with the practices, to facilitate chemical knowledge acquisition in non-chemical engineering majors. Teaching reforms such as using a variety of teaching methods and evaluation modes were employed in oil & gas storage and transportation engineering major, which has received significant teaching results.     

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

Resonance‐assisted hydrogen bonding (RAHB), a concept introduced by Gilli and co‐workers in 1989, concerns a kind of intramolecular H‐bonding strengthened by a conjugated π‐system, usually in 6‐, 8‐, or 10‐membered rings. This Review highlights the involvement of RAHB as a driving force in the synthesis of organic, coordination, and organometallic compounds, as a handy tool in the activation of covalent bonds, and in starting moieties for synthetic transformations. The unique roles of RAHB in molecular recognition and switches, E/Z isomeric resolution, racemization and epimerization of amino acids and chiral amino alcohols, solvatochromism, liquid‐crystalline compounds, and in synthons for crystal engineering and polymer materials are also discussed. The Review can provide practical guidance for synthetic chemists that are interested in exploring and further developing RAHB‐assisted synthesis and design of materials.     

Development of a novel electrochemical cell for slab optical waveguide spectroscopy for in situ observation of methylene blue and anions on an electrode/electrolyte interface

A new spectroelectrochemical cell for slab optical waveguide (SOWG) spectroscopy was developed in order to observe in situ an electrode/electrolyte interface for bulk electrolysis. The new SOWG spectroelectrochemical cell has been evaluated by simultaneous electrochemical-absorption experiments of methylene blue (MB) using cyclic voltammetry (CV) and SOWG spectrometry. CV was performed in the SOWG spectroelectrochemical cell using indium tin oxide (ITO) coated glass as the working electrode, platinum wire as the counter electrode and a silver/silver chloride electrode (Ag/AgCl) as the reference electrode. Based on the CV and SOWG spectrometric data, it was found that the SOWG spectra showed the MB spectra on the electrode surface selectively and that SOWG with the cell would be useful as a tool for in situ study of an electrode/electrolyte interface. Using this cell, the effects of the supporting electrolytes, NaNO₃, KNO₃, CH₃COONa, and CH₃COOK on the absorbance of MB were examined at the potential of +0.8 V versus Ag/AgCl. The decrease in MB absorbance by nitrate ions was greater than that of acetate ions. Therefore the competitive adsorption of nitrate ions was stronger than that of acetate ions. Thus, the decrease in absorbance of MB in the presence of anions demonstrates the competitive adsorption of anions. These results show that the extent of specific adsorption of electrolytes was observed by measuring the SOWG absorbance intensity of MB.