Multidimensional Analytical Techniques for Studying the Thermo-Oxidative Degradation of Impact Poly(propylene)

Summary: Impact poly(propylene) copolymers (ICPP) are complex polymer systems containing various types of ethylene-propylene copolymers as well as the majority poly(propylene) phase. In this study, multidimensional analytical techniques are applied to study the thermo-oxidative degradation of these complex materials. The combination of size exclusion chromatography (SEC) and FTIR via an LC-transform interface allows for the identification and tracking of the low molecular weight oxidized products. The degradation has a significant effect on the crystallisability of the material. DSC analysis shows that as the degradation proceeds, there is a significant decrease in the onset of the melt endotherm as well as the development of a double melt peak and peak broadening. Preparative Temperature Rising Elution Fractionation (TREF) is used to isolate the various fractions according to crystallisability during the polymer degradation. TREF-SEC and TREF-(SEC-FTIR) allows for the isolation and identification of the polymer fractions undergoing oxidative degradation. It is shown that these multidimensional analytical techniques using crystallisability in the first dimensional fractionation provide more information on the mechanism and process of oxidative degradation than traditional bulk analysis methods.     

Quantitative confirmation of the crystal-amorphous interphase in semicrystalline poly(vinylidene fluoride) and poly (vinylidene fluoride)/poly (ethyl methacrylate) blends

Dielectric and thermal characterizations were performed for poly (vinylidene fluoride) (PVDF)/poly (ethyl methacrylate) (PEMA) blends of different composition. The characteristics of PVDF β relaxation were shown to be little affected in the semicrystalline blends with PEMA. The relaxation strength, however, depends strongly on the PEMA content and a linear relation was found between the intensity of the β relaxation and the weight fraction of the PVDF crystal-amorphous interphase. Phase structures of the PVDF/PEMA blends are also proposed. © 1994 John Wiley & Sons, Inc.     

串级质谱应用于蛋白质科学研究的实例介绍

串级质谱（MS/MS）分析是近年来迅猛发展的仪器分析技术,对于化学相关学科与其他交叉领域都起到了极大的推动作用。在使用计算机辅助解析后,常常需要进一步进行图谱指认,而这部分内容常常被化学教学所忽略。从串级质谱的原理出发,详细分析了肽段在二级质谱中可能的断裂模式与结构特性,并进一步以模型蛋白为例详细分析了串级质谱的图谱指认和峰的归属的基本原理与实用性方法,以期对教学与科研有助。     

[Hg(SCN)4]2-对蛋白质的荧光猝灭反应及其分析应用

在pH=1.4~3.4的酸性介质中, [Hg(SCN)4]2-配阴离子可与牛血清白蛋白(BSA)、 γ-球蛋白(γ-G)和血红蛋白(Hb)等蛋白质反应形成复合物, 从而引起蛋白质荧光的猝灭. 荧光猝灭的程度在一定范围内与Hg(Ⅱ)的浓度呈线性关系, 可用于Hg(Ⅱ)的测定. 该方法有较高的灵敏度, 检出限(3σ)分别为4.4 ng/mL(BSA)、 6.5 ng/mL(γ-G)和12.9 ng/mL(Hb), 其中以BSA体系灵敏度最高. 研究了[Hg(SCN)4]2-与蛋白质相互作用对荧光光谱的影响、 适宜的反应条件和影响因素; 结合吸收光谱的变化、 温度的影响以及某些热力学参数讨论了荧光猝灭反应的机理; 并以[Hg(SCN)4]2--BSA体系为例考察了共存物质的影响. 结果表明, 该方法具有良好的选择性. 以BSA为探针采用荧光猝灭法测定了红药水中汞溴红和乙肝疫苗中硫柳汞的含量, 结果令人满意.     

Analytical properties of 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone: simultaneous spectrophotometric determination of copper(II) and nickel(II) in edible oils and seeds

The analytical properties of 1-phenyl-1,2-propanedione-2-oxime thiosemi-carbazone (PPDOT) are described for the first time. The reagent gives colour reactions with copper(II) and nickel(II) in sodium acetate-acetic acid buffer medium. The copper complex shows maximum absorbance at 465 nm while the nickel complex at 395 nm. Therefore, these colour reactions have been advantageously used for the simultaneous spectrophotometric determination of copper(II) and nickel(II) in synthetic mixture and also in edible oils and seeds.     

聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸盐热电性能的 提升策略研究进展

近十年,有机聚合物及其复合热电材料与柔性器件取得了显著进展,在废热回收利用、可穿戴电子学、软体机器人和物联网等领域有广泛的应用.其中,聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)是迄今研究最多也是性能最高的聚合物体系.本文对近年来有关PEDOT:PSS热电性能有效提升主要策略的文献报道进行了总结.首先,从PEDOT:PSS的二次掺杂/去掺杂、酸或碱处理和离子液体处理方面等,重点论述了掺杂/去掺杂策略的研究进展;然后,分别从改善聚集态结构、构筑PEDOT微纳米结构和与碳纳米材料复合等3个方面,重点介绍了采用此3种策略提升PEDOT:PSS热电性能的研究进展;最后,对该领域进行总结,提出了开展进一步研究的建议,并对其未来发展前景进行展望.     

Current Scenario of Poly (2,5-Benzimidazole) (ABPBI) as Prospective PEM for Application in HT-PEMFC

Abstract

In last two decades, acid doped polybenzimidazole as polymer electrolyte membrane (PEM) has been widely recognized and envisioned as “ideal” proton conducting materials for application in high temperature PEM fuel cell (HT-PEMFC). The majority of research and developmental work is mainly focused on poly (2,2´-m-phenylene-5,5´-bibenzimidazole), However, it is neither easy-processed nor inexpensive component of the respective family. On the other hand, among the various members belonging to benzimidazole family, poly (2,5-benzimidazole) is unique because it possesses a cost-attractive, single-step synthesis process, high extent of doping as well as good chemical and thermal stability. In the recent years this material has proved its potency in the earlier research. Thus this review puts special emphasis on poly (2,5-benzimidazole) and epitomizes the on-going breath-taking progress and achievements on the fabrication of poly (2,5-benzimidazole) based membranes. The write-up describes the effect of blending, cross-linking, ionic liquids and incorporation organic/inorganic nano-fillers. In addition, incorporating other protonic dopants such as heteropoly acids into the chain of poly (2,5-benzimidazole) molecular skeleton is also overviewed. Moreover, the critical interpretation of different causes responsible for earlier degradation and their effect towards the fabrication of high temperature membrane electrode assembly are visualized herein.

• Highlights

• Current developments and existing challenges of ABPBI in PEMFC have been reviewed.

• PEM Modification and addition of protonic dopants has been discussed.

• Proton migration, permeability, stability and reliability are thoroughly illustrated.

• Different ABPBI-based membranes and their performance are comparatively analyzed.

     

新型荧光试剂1-(8-喹啉)-3-(3,5-二溴-2-吡啶)-三氮烯的合成及其应用

将具有荧光特性的杂环8-氨基喹啉和吡啶类试剂结合,并引入三氮烯结构,合成了新型荧光试剂1-(8-喹啉)-3-(3,5-二溴-2-吡啶)-三氮烯(QBPyT)。其结构经元素分析、红外光谱、核磁共振波谱证实。研究结果表明,在pH 9.5硼酸-氢氧化钠缓冲溶液的介质存在下,该试剂在λex/λem=248nm/496nm处产生强荧光,并且能与铅(Ⅱ)形成配合物从而使荧光增强。据此建立了三氮烯测定铅(Ⅱ)的新型荧光分析法。铅的浓度在5.0×10-7～1.2×10-5 mol.L范围内与其荧光强度呈线性关系,检出限(3S/N)为9.5×10-8 mol.L。将其应用于水样中铅(Ⅱ)的测定,测得回收率在92.6%～94.0%之间,测定值的相对标准偏差(n=5)小于3.5%。     

钯(II)-柠檬黄-离子液体三元络合体系的共振瑞利散射光谱及其分析应用研究

在pH 2.0～6.0的BR缓冲溶液中, Pd(II)与柠檬黄(TTZ)形成的络离子与溴化1-十六烷基-3-甲基咪唑([C₁₆mim]Br)离子液体发生作用形成离子缔合物, 引起溶液共振瑞利散射(RRS)显著增强, 并产生新的RRS光谱, 其最大RRS峰位于458 nm. 在0.043～0.860 μg/mL范围内散射强度(ΔI)与柠檬黄的浓度成正比. 该方法简单灵敏, 对柠檬黄的检出限(3σ/K)为5.5 ng/mL (n＝11). 建立了一种简便、快速测定柠檬黄的新方法, 并成功用于饮料样中柠檬黄含量的测定.     

Analytical separation of antimony(III) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) with cyanex 302

A method is proposed for the separation of antimony(III) (100–400 g) from bismuth(III), lead(II), gallium(III), thallium(III), tellurium(IV) and tin(IV) from an aqueous solution of pH 0.5–1.5 using 8×10^–3–1×10^–2 mol dm^–3 cyanex 302 dissolved in toluene as an extractant. The antimony is stripped from the cyanex phase with water and determined spectrophotometrically with iodide. Various experimental parameters are optimized and the probable 13 stoichiometry of the extracted species is evaluated. The method is applicable to the analysis of alloys and pharmaceutical samples. The separation and determination take only 20 min.     

Studying Effect of Typical Nonplanar Cyclic Alcohols (n = 5‐7) on Micellization of Sodium Dodecyl Sulfate (SDS) in Aqueous Solution and Locating Their Solubilization Site in SDS Micelles

Cyclic alcohols (n = 5‐7) are compounds of distinctive nonplanar structure. Effect of the alcohols on micellization of sodium dodecyl sulfate (SDS) in aqueous solution are examined by determining the critical micelle concentration (CMC) by conductometry and the micelle aggregation numbers (N_agg) by fluorometry, respectively. In general, the CMC of SDS decreases with increase in volume of a cyclic alcohol in water and increases further after attaining a minimum value. The N_agg of SDS varies little with small addition of a cyclic alcohol, but decreases when added in sufficient volume. Both the changes of the CMC and N_agg with carbon number in the ring of the alcohols occur irregularly due to their steric reasons and nonplanar nature. The irregularity makes a difference between the cyclic alcohols and their chain counterparts. Based on ¹H NMR chemical shift measurements, the cyclic alcohols are found to be solubilized in the palisade layer in SDS micelles.     

Electrochemiluminescence Characterization of Poly(luminol‐benzidine) Composite Films and Their Analytical Application

A composite film of poly(luminol‐benzidine) was prepared on the graphite electrode surface by electropolymerizing luminol and benzidine in acidic medium. It was found that the poly(luminol‐benzidine) composite film presented better electrochemiluminescence (ECL) analytical performances for H₂O₂ than that of the polyluminol film. Based on these findings, a more sensitive ECL sensor for H₂O₂ was developed. At the same time, our investigating results on this composite film revealed that, as a real ECL luminophor in this composite film, the polymeric 3‐aminophthalate presented higher fluorescence quantum yield than that in the pure polyluminol film, which suggested that the excellent ECL performances of the composite film may originate from the enhancement of the ECL luminophor quantum yield. Based on these results, a new method to improve the ECL analytical performances of the polymeric luminol was also proposed.     

Flow-Injection Chemiluminescence as a Means of Studying the Metabolism of Unbound Chromium(III) in Rabbit Blood with On-Line Microdialysis Sampling

In this paper, we present an in-vivo, on-line, real-time analytical system for monitoring the metabolism of free chromium(III) in rabbit blood. This system includes microdialysis sampling, ion-exchange on-line separation and chemiluminescence detection. The results show that none of the co-existing substances in the blood, including protein and other small molecules, interfere with the determination. CrCl₃·6H₂O was administrated orally (0.5 g), and the microdialysis probe was utilized to sample rabbit blood with a perfusion rate of 10 µL min⁻¹. The dialytic efficiency of chromium(III) under the experimental conditions was 18.1 ± 5.1% (n=3). The concentration-time curve of chromium(III) is in accordance with the one-compartmental open model, the T_1/2 is 16.62 min.     

Spectrophotometric Determination of Trace Chromium(VI) in Mass Chromium(III)

There is little conclusive evidence of the toxic effects of Cr(III) so far, but Cr(VI) has carcinogenic activity, so the analysis of the chromine ions is very important in environmental research and the quality control of industry products. Usually Cr(III) and Cr(VI) interfere with each other in the species analysis, the measurement of Cr(VI) of numerous previous papers is related to the Cr(VI) samples, which contain a little Cr(III). When the amount of trivalent chromine exceeds ten …     

Solid-phase extraction and preconcentration of cadmium(II) in aqueous solution with Cd(II)-imprinted resin (poly-Cd(II)-DAAB-VP) packed columns

A novel chelating resin (poly-Cd(II)-DAAB-VP) was prepared by metal ion imprinted polymer (MIIP) technique. The resin was obtained by one pot reaction of Cd(II)-diazoaminobenzene-vinylpyridine with cross-linker ethyleneglycoldimethacrylate (EGDMA). Comparing with non-imprinted resin, the poly-Cd(II)-DAAB-VP has higher adsorption capacity and selectivity for Cd(II). The distribution ratio (D) values for the Cd(II)-imprinted resin show increase for Cd(II) with respect to both D values of Zn(II), Cu(II), Hg(II) and non-imprinted resin. The relatively selective factor (α_r) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II), are 51.2, 45.6, and 85.4, which are greater than 1. poly-Cd(II)-DAAB-VP can be used at least 20 times without considerable loss of adsorption capacity. Based on poly-Cd(II)-DAAB-VP packed columns, a highly selective solid-phase extraction (SPE) and preconcentration method for Cd(II) from aqueous solution was developed. The MIIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 30 μg l⁻¹. The detection limit and quantification limit were 0.093 and 0.21 μg l⁻¹ (3σ) for flame atomic absorption spectrometry (FAAS). The relative standard deviation of the eleven replicate determinations was 3.7% for the determination of 10 μg of Cd(II) in 100 ml water sample. Determination of Cd(II) in certified river sediment sample (GBW 08301) demonstrated that the interfering matrix had been almost removed during preconcentration. The column was good enough for Cd(II) determination in matrixes containing components with similar chemical property such as Cu(II), Zn(II) and Hg(II).     

C60和C70在几种溶剂中的溶解度与温度的关系

溶解度是富勒烯C6O和C7O的基本物理化学常数之·．自电弧法合成富勒烯成功以后＊；人们就很重视C60和C7O在各种溶剂中的溶解性能．由于在分离、分析富勒烯和研究其化学反应时，往往是在溶液中进行的，因此，不少科学家很快就测定TC60和C70室温下在多种有机溶剂中的溶解度［’－     

Potentiometric determination of silver(I), palladium(II) and gold(III) in mixtures by use of an iodide-selective electrode

Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys.     

Spectrophotometric Simultaneous Determination of Zinc(II), Manganese(II) and Iron(II) in Pharmaceutical Preparations Using OSC-PLS

The purpose of this paper is to develop a fast and sensitive spectrophotometric method for the simultaneous determination of zinc(II), manganese(II) and iron(II) in pharmaceutical preparations. The method presented in this work is based on the well-known reaction of these ions with 4-(pyridylazo)resorcinol (PAR)1. The application of quantitative chemometric methods, particularly PLS to multivariate chemical data is becoming more widespread owing to the availability of digitized spectroscop…     

Multidimensional Gas Chromatography Coupled On-Line with Isotope Ratio Mass Spectrometry (MDGC-IRMS): Progress in the Analytical Authentication of Genuine Flavor Components

Multidimensional gas chromatography coupled on-line with isotope ratio mass spectrometry (MDGC-IRMS) is presented as a powerful method for origin-specific analysis. Scope and limitations of this sophisticated coupling technique are discussed with regard to accuracy and precision.     

PVB存在下PVC化学法脱氯化氢的研究

ＰＶＢ存在下ＰＶＣ化学法脱氯化氢的研究刘恒＊李大成陈朝珍（四川联合大学化工学院成都６１００６５）关键词聚氯乙烯，脱氯化氢，聚乙烯醇缩丁醛１９９６－０９－０８收稿，１９９７－０５－２６修回国家教育委员会留学归国人员资助费资助课题近年来在ＰＶＣ脱氯化氢制...