实验化学的名师巨匠——本生

本生是一代实验化学的名师巨匠,他的一生在化学发展史上留下了光辉的一页。在几十年的科学实验和研究中,他潜心钻研化学理论,不断提高自己的实验技能。他亲自设计和改进了诸多实验仪器和装置,并为此做出了发明和创造。他的主要贡献有:创立了光谱分析法,发现了铯和铷两种元素,发明了本生灯和本生电池,并在化学工业的掘起和发展中做出了重要的贡献。     

Spin-Free理论与Woodward-Hoffmann规则——丁二烯体系电环合反应的研究

用Spin-Free理论,对丁二烯体系电环合反应进行了研究,得到了基态和各激发态的位能面,解释了加热和加光反应机理和选择定则,对其中的单态和三态光化反应作了初步探讨并求出了有关的活化能。     

花粉蛋白和多糖的研究

从葡萄和罂粟花粉中分别纯化得RP3I和PSPP1-4肽, 测定了它们的生理活性,并合成了PSPP1以外的肽, 从Typha Angustifilia和codonopsis pilosula花粉获得了TA-C和CPA-E多糖, 并研究了它们的部份特征和结构。     

新型大环超分子化学:从杂杯芳烃到冠芳烃——纪念黄志镗先生诞辰90周年

本文介绍了杂杯芳烃和冠芳烃的研究起源,总结了杂杯芳烃和冠芳烃的设计与合成、构象和大环空腔结构特征,展示了杂杯芳烃和冠芳烃的分子识别和组装性质,概述了杂杯芳烃和冠芳烃在功能材料的制备中的应用,展望了大环超分子化学未来的发展方向。     

钙钛矿型高温质子导体研究进展

介绍了钙钛矿型和复合钙钛矿型化合物的结构、常用的制备方法和传导性质,详细分析了其传导机理,评述了其研究进展和在气体传感器、固体燃料电池、有机物加氢和脱氢以及常压电化学合成氨等方面的应用,展望了应用前景和发展趋向.     

环氧乙烷和环氧丙烷开环聚合

环氧乙烷和环氧丙烷的开环聚合产物在表面活性剂工业和聚氨酯工业得到了极为广泛的应用.本文综述了近几年来发展的用于环氧乙烷和环氧丙烷开环聚合的各类催化剂体系,分别讨论了各类催化剂体系对环氧乙烷和环氧丙烷的不同作用机制,考察了反应物结构对反应活性和选择性的影响,重点介绍了配位络合催化剂体系在环氧乙烷和环氧丙烷开环聚合反应中的应用,并指出了今后研究的方向.     

我国金属中气体分析的回顾

近几年来,我国金属中气体分析得到了很大的发展。使用了一些新的技术和方法;研制了各种型号的新仪器,制定了部分标准方法和制备了部分标准试样。同时召开了数次全国性和地区性的报告会和鉴定会,肯定了成果,交流了经验。本文仅就我国金属中气体分析的进展作一简要的回顾。一、热源和测试方法我国金属中气体(指氧、氮、氢)分析,开展较早的单位是科学院金属研究所、有色总公司北京有色金属研究总院和冶金部钢铁研究总院。他们在50年代就建立了真空熔融微压法的实验装置,开展了黑     

聚合物形状记忆材料的研究进展

聚合物形状记忆材料作为一种重要的刺激响应材料,近10年内得到了快速的发展,出现了新的分类方向,机理解释、转变结构和应用。在航空航天、传感制动和生物医药等领域展现了优越的性能,研究成果受到了学术和工业上的极大重视,成为当今最富有活力的研究领域之一。本文全面总结了近期国内外学者对聚合物形状记忆材料的研究进展,阐述了聚合物形状记忆材料的记忆机理及分类和功能应用,并探讨了未来的研究前景和方向,以期为聚合物形状记忆材料的研究提供参考。     

XNCS→XSCN (X=Cl,Br)异构化的实验与量子化学研究

捕获得到了纯净化合物ClSCN和BrSCN紫外光电子能谱图,OVGF方法计算的ClSCN和BrSCN的电离能与实验值吻合很好,并用该方法首次预测了ClNCS和BrNCS的电离能．讨论了XNCS→XSCN(X=Cl,Br)的异构化过程,首次优化得到了四元环过渡态的构型．着重从电子密度拓扑分析计算了反应进程中的各点,讨论了反应进程中键的断裂和生成,上述反应都经历了三元环过渡结构,找到了这类反应的“能量过渡态”和“结构过渡态”．     

钢液中喷吹稀土合金粉剂的试验研究

介绍电炉和氧气顶吹转炉炼钢钢液中喷吹RE-Si-Fe和Ca-Si粉剂的试验结果。钢液中喷吹RE-Si-Fe和Ca-Si混合粉剂有效地改变了钢中夹杂的形态、大小和分布,细化了晶粒,改善了钢的低倍组织,从而减小了钢材的各向异性,提高了钢材的综合机械性能。     

Comparison of extraction techniques for the isolation of explosives and their degradation products from soil

A comparison of four extraction techniques used for the isolation of 14 explosive compounds (Method 8330-Explosives) from spiked soil samples is described. Soxhlet warm extraction (SWE), pressurized solvent extraction (PSE), microwave assisted extraction (MAE) and supercritical fluid extraction (SFE) were included. The effects of basic extraction conditions – i.e. type of extraction solvent, temperature, pressure, and extraction time – were investigated. The best extraction recovery of the monitored compounds from spiked soil was obtained using pressurized solvent extraction. Recoveries of explosives using the PSE technique were in the range from 65 to 112%. Extraction recoveries by Soxhlet warm extraction and supercritical fluid extraction reached 65–99% and 52–75%, respectively. The lowest extraction recoveries (28–65%) were obtained using microwave assisted extraction. A very low extraction recovery for tetryl was observed in all cases but the best results were achieved by pressurized solvent extraction (58%).     

Equilibrium and Kinetic Aspects of Hg(II) Extraction from Natural Waters with Diphenylthiocarbazone

A diphenylthiocarbazone (dithizone) based liquid-liquid extraction method of general utility is proposed for small-scale Hg(II) extraction from natural waters. The quantitative aspects related to the extraction are studied in terms of distribution of mercury dithizonate in carbon tetrachloride-water system at 293 K (20±1°C). Various distribution constants related to the reagent and the complex formed are evaluated. The equilibrium and kinetic studies of extraction and complex formation are analytically based on atomic absorption and colorimetric methods. Local natural waters were subjected to the proposed method for Hg(II) removal. The method is found to be capable of removing above 98% mercury in a single-step extraction under the conditions evaluated in terms of matrix pH, equilibration time and amount of reagent.     

Comparison of Extraction Techniques and Surfactants for the Isolation of Total Polyphenols and Phlorotannins from the Brown Algae Lobophora variegata

Abstract

Surfactant-mediated extraction (SME), pressurized liquid extraction (PLE), and enzyme-assisted extraction (EAE) have been compared to improve the isolation of phlorotannins from the brown algae Lobophora variegata. Enzymatic treatment with Alcalase 2.4?L FG, Carezyme 4500?L, protease from Streptomyces griseus, pectinase from Aspergillus niger, Celluclast 1.5?L, protease from Bacillus licheniformis; surfactant extraction with triacetin and guaiacol and PLE with ethanol:water as extracting solvent, have been studied in terms of total phenolic content by the Folin–Ciocalteu method and total phlorotannin content using the DMBA assay. The results showed that SME yields the highest amount of phenols and phlorotannins by using food grade guaiacol as the surfactant. An extraction protocol was developed to maximize the amount of extract obtained from L. variegata. The effects of various parameters such as the type of surfactant, efficacy of surfactant, and optimum pH, on the extraction efficiency of polyphenols were examined. The simultaneous use of the enzyme and surfactant was also investigated. However, a synergistic effect between the enzymes and the surfactant for the extraction of polyphenols has not been observed. Considering total phenols and total phlorotannins in the extract, the extraction yield were obtained for total phenols as SME?>?EAE?>?PLE and for total phlorotannins as SME?>?PLE?>?EAE.     

Comparison of extraction techniques for isolation of steroid oestrogens in environmentally relevant concentrations from sediment

The comparison of four extraction techniques for isolation of five native and one labelled steroid oestrogens from sediment was described. The three conventional extraction techniques Soxhlet warm extraction (SWE), accelerated solvent extraction (ASE), microwave-assisted extraction (MAE) and a promising technique QuEChERS were tested for isolation of low environmentally relevant oestrogen concentrations using different extraction conditions. The least expensive and time-consuming method QuEChERS provided the best extraction recoveries (53–84%) from all techniques. MAE achieved the highest recovery from conventional techniques for less polar oestrogens using dichloromethane: acetone 3:1 mixture as an extraction solvent (50–71%), but for extraction of the whole group of oestrogens including more polar estriol acetone or methanol must be used. ASE provided higher extraction recoveries using dichloromethane at 60°C (53–74%) for less polar oestrogens. However, the repeatability of results was unsatisfactory and recoveries using other extraction conditions were lower than for MAE. The most time-consuming SWE achieved the worst extraction recoveries and for isolation of low oestrogen concentrations from sediments, it is completely unsuitable.     

Effect of Extraction Procedures with Ultrasound and Cellulolytic Enzymes on the Structural and Functional Properties of Citrus grandis Osbeck Seed Mucilage

The structural and functional properties of Citrus grandis Osbeck (CGO) seed mucilage by different extraction practices, including conventional citrate buffer, ultrasonic-assisted (UAE), enzymatic-assisted extraction (EAE) with cellulase or Celluclast^® 1.5 L and various ultrasonic-assisted enzymatic extraction (UAEE) procedures were investigated. It was found that CGO seed from agricultural and processing byproducts is an excellent new source of high methoxyl pectin with quite high intrinsic viscosity (about 108.64 dL/g) and molecular weight (about 1.9 × 10⁶) as compared with other pectin sources. UAEE with Celluclast^® 1.5 L enhanced the extraction yield most pronouncedly (about 2.3 times). Moreover, the monosaccharide composition of CGO seed mucilage is least affected by EAE with Celluclast^® 1.5 L. In contrast, EAE with cellulase dramatically reduces the galacturonic acid (GalA) content to less than 60 molar%, and increases the glucose (Glc) content pronouncedly (to about 40 molar%), which may be considered as an adverse effect in terms of pectin purity. Though extraction procedures involved with ultrasound and cellulolytic enzymes generally show a decrease in GalA contents, weight average molar mass and intrinsic viscosity, EAE with Celluclast^® 1.5 L is least affected, followed by UAE and UAEE with Celluclast^® 1.5 L. These features can be leveraged in favor of diversified applications.     

Comparison of extraction methods for sampling of low molecular compounds in polymers degraded during recycling

The demand for mechanical recycling of plastic waste results in an increasing amount of recycled polymeric materials available for development of new products. In order for recycled materials to find their way into the material market, high quality is demanded. Thereby, a complete and closed loop of polymeric materials can be achieved successfully. The concept of high quality for recycled plastics imply that besides a pure fraction of e.g. polyethylene (PE) or polypropylene (PP), containing only minor trace amount of foreign plastics, knowledge is required about the type and amount of low molecular weight (LMW) compounds. During long-term use (service-life), products made of polymeric materials will undergo an often very slow degradation where a series of degradation products are formed, in parallel, additives incorporated in the matrix may also degrade. These compounds migrate at various rates to the surrounding environment. The release rate of LMW products from plastics depends on the initiation time of degradation and the degradation mechanisms. For polymers the formation of degradation products may be initiated already during processing, and subsequent use will add products coming from the surrounding environment, e.g. fragrance and aroma compounds from packaging. During recycling of plastics, emissions which contain a series of different LMW compounds may reach the environment leading to unwanted exposure to additives and their degradation residues as well as degradation products of polymers.Several extraction techniques are available for sampling of LMW compounds in polymers before chromatographic analysis. This paper reviews and compares polymer dissolution, accelerated solvent extraction (ASE), microwave assisted extraction (MAE), ultrasound assisted extraction (UAE), super critical fluid extraction (SFE), soxhlet extraction, head-space extraction (HS), head-space solid phase micro extraction (HS-SPME), and head-space stir bar sorptive extraction (HSSE) as appropriate sampling methods for LMW compounds in recycled polymers. Appropriate internal standards useful for these kinds of matrices were selected, which improved the possibility for later quantification. Based on the review of extraction methods, the most promising techniques were tested with industrially recycled samples of HDPE and PP and virgin HDPE and PP for method comparison.     

固相萃取技术在食品痕量残留和污染分析中的应用

食品痕量残留和污染分析中,样品的前处理极为重要,也是其难点所在。由于食品和农产品样品的多样性和复杂性,目前还没有一种前处理技术能够适合所有情况下的所有样品。本文对近年来发展起来的新型固相萃取技术如固相微萃取、搅拌棒吸附萃取、基质固相分散萃取、分子印迹固相萃取、免疫亲和固相萃取、整体柱固相萃取、碳纳米管固相萃取等在食品痕量残留和污染分析中的应用进行了综述,对未来的发展前景作了展望。     

Application of water as a solvent in microwave-assisted extraction for analysis of PCBs and CBzs in fly ash

Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE.     

Sequential Extraction of Natural Surface Coatings: Comparison with Single Stage Extraction and Its Application in Investigating Adsorption Characteristics of Surface Coating Components for Metals

Multistage sequential extraction with different sequences was applied to extracting natural surface coatings( NSCs), and the results were compared with those by single stage extraction technique. The optimal sequential extraction scheme with the best performance was selected and incorporated into the method of selective extraction followed by adsorption and statistic analyses to study the adsorption parameters of Fe oxides, Mn oxides and organic matters in NSCs for Pb and Cd, to validate the applicability of the sequential extraction scheme. The Langmuir adsorption parameters of each component of surface coating estimated according to the adsorption data of single stage extraction of NSCs were all similar to those of sequential extraction of NSCs, and the maximum difference between the metal adsorption abilities of the components estimated via the two extraction techniques was only about 20%, indicating that either extraction techniques could be used. The optimal sequential extraction scheme obtained was first extracted with NH₂OH·HCl, then with Na₂S₂O₄, and finally with oxalic acid.     

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.