刚性侧链型液晶高分子与含二维液晶基元的液晶高分子

提出了“刚性侧链型液晶高分子”与“含二维液晶基元的液晶高分子”两个新概念。     

Isotope-dilution ICP–MS for trace element determination and speciation: from a reference method to a routine method?

This critical review discusses the conditions under which inductively coupled plasma–isotope dilution mass spectrometry (ICP–IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP–IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP–IDMS suffer both from lack of commercially available isotope-labeled spike compounds for species-specific isotope dilution and from the more complicated system set-up required for species-unspecific ICP–IDMS analysis. Coupling of gas or liquid chromatography with species-specific ICP–IDMS, however, enables validation of analytical methods involving species transformations which cannot easily be performed by other methods. The potential and limitations of ICP–IDMS are demonstrated by recently published results and by some unpublished investigations by our group. It has been shown that possible loss of silicon as volatile SiF₄ during decomposition of a sample by use of hydrofluoric acid has no effect on trace silicon determination if the isotope-dilution step occurs during digestion in a closed system. For powder samples, laser ablation ICP–IDMS can be applied with an accuracy comparable with that only available from matrix-matched standardization, whereas the accuracy of electrothermal vaporization ICP–IDMS was strongly dependent on the element determined. The significance of easy synthesis of isotope-labeled spike compounds for species-specific ICP–IDMS is demonstrated for monomethylmercury and Cr(VI). Isotope-exchange reactions between different element species can prevent the successful application of ICP–IDMS, as is shown for iodinated hydrocarbons. It is also shown for monomethylmercury that species transformations during sample-pretreatment steps can be followed by species-specific ICP–IDMS without loss of accuracy. A relatively simple and time-efficient procedure for determination of monomethylmercury in environmental and biological samples is discussed. The method, which entails a rapid microwave-assisted isotope dilution step and in-situ extraction of the derivatized species, has good potential for routine application in the future.     

刚性有机填料同时增韧增强改性硬PVC韧性体的研究

刚性有机填料(简称ROF)是用作塑料改性剂的刚性有机聚合物,如PS、PMMA、SAN等。实验发现将少许ROF填充到硬聚氯乙烯韧性体中,能使基体的冲击强度和拉伸强度同时提高,获得既增韧又增强的双重效果。克服了传统的弹性体增韧改性损害基体强度的缺陷。     

Microchip Capillary Electrophoresis‐Electrochemistry with Rigid Graphite‐Epoxy Composite Detector

A new rigid graphite‐epoxy composite electrode for electrochemical detection in microchip electrophoresis is described. The end‐column wall‐jet detection design relying on tubular rigid composite working electrode shows favorably low noise level and high signal‐to‐noise ratio when compared to glassy carbon detector. The performance of rigid graphite‐epoxy composite detector was compared to glassy carbon detector using dopamine and catechol as model analytes. The various parameters of the microchip electrophoresis‐rigid graphite‐epoxy composite detector were optimized.     

广州市夏、冬季室内外PM2.5中元素组分的特征与来源

通过采集广州市9个居民住宅室内、外的PM2.5样品,测定分析PM2.5中18个元素组分的质量浓度,分析讨论其污染、分布特征并解析其污染来源。经过比较得知,广州市PM2.5中元素污染较严重;不同类型住宅PM2.5中元素浓度存在空间分布特征;大部分元素浓度具有夏季比冬季低的变化特征;室内与室外元素浓度比值介于0.4974～2.0497之间;元素浓度的室内、室外相关拟合结果说明冬季室内空气受室外空气影响比夏季时情况更明显;基于富集因子分析,Se、As、S、Pb、Br、Zn和Cl元素高度富集;Ni、V、Cu元素中等富集,主要来自人为源,而Cr、Sr、K、Mn、Ca和Ti元素不富集,主要来自自然源。     

矿物药中无机元素分布浅析

矿物药主要包括天然矿物,生物化石、加工品及纯粹化学制品学,主要成分均为无机化合物,依矿物中所含的主要或含量最多的元素和化合物分为九类,《矿物药与丹药》将矿药分为十种,根据矿物药中所含有效成分中可测元素分为十类。通过给矿物药分类,便于研究矿物药的理化性质,分析其有效成分或主要成分,探讨药理作用,明确主治范围,为寻求新药,开展新剂型创造条件。     

Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金电极腐蚀行为研究

研究了Pd部分替代Mg对Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金腐蚀性能的影响. 利用机械合金化方法制备了Mg0.9－xTi0.1PdxNi(x=0.04～0.1)贮氢合金. XRD和TEM分析表明经120 h球磨后该合金完全非晶化. 循环充放电测试结果表明, Pd的替代有效地延长了Mg0.9－xTi0.1PdxNi(x=0.04～0.1)合金的循环寿命. 采用开路电位测量, 阳极极化, 电化学阻抗和X射线光电子能谱研究了该合金的腐蚀行为. 结果表明, 随着Pd含量增加, 合金腐蚀电位正移, 初始腐蚀电流下降, 腐蚀电流增加的速度变缓. 采用本文提出的等效电路模型较好地拟合了合金的电化学阻抗谱. 分析表明, 随着Pd含量的增加, 合金表面钝化膜厚度和电阻逐渐增大. X射线光电子能谱分析表明, Pd的加入减弱了合金在充放电过程中的氧化程度. 当Pd含量达到0.1时, Mg0.9－xTi0.1PdxNi(x=0.04～0.1)合金的耐腐蚀性能最好, 其放电容量保持率最高.     

含联萘基元的刚性环状齐聚物手性孔穴的振动圆二色谱研究

纳米尺度刚性环状齐聚物因其具有独特的孔穴结构,在基础与应用研究中引起了人们的广泛关注.当具有功能基团的分子骨架形成环状结构时,这种功能分子孔穴在分子识别及主-客体化学等方面具有广阔的应用前景.含有手性基团的手性大环分子具有特定的手性孔穴,在手性拆分、手性识别等方面引起了各国研究者的兴趣.     

Multi-element selective radio frequency plasma detector for capillary gas chromatography

A radio frequency plasma detector for element specific detection in gas chromatography is described. The detector is comprised of a radio frequency (300 kHz) discharge between electrodes in helium, and utilizes a low-resolution emission spectrometer to monitor selected spectral emission lines produced when the helium discharge decomposes and excites the atomic constituents in the chromatographic column effluent. The spectrometer is tuned to an atomic emission line in the near-infrared portion of the spectrum, and the emission intensity from the discharge region of a selected line is used to monitor the concentration of the element producing that line. Acceptable detector sensitivity was achieved by the use of a high-throughput optical system. Selectivity was achieved by a combination of correct line selection, plasma and carrier gas purification, and plasma gas doping.     

The amount of immobilized polymer in PMMA SiO2 nanocomposites determined from calorimetric data

For semicrystalline polymers there is an ongoing debate at what temperature the immobilized or rigid amorphous fraction (RAF) devitrifies (relaxes). The question if the polymer crystals are melting first and simultaneously the RAF devitrifies or the RAF devitrifies first and later on the crystals melt cannot be answered easily on the example of semicrystalline polymers. This is because the crystals, which are the reason for the immobilization of the polymer, often disappear (melt) in the same temperature range as the RAF. For polymer nanocomposites the situation is simpler. Silica nanoparticles do not melt or undergo other phase transitions altering the polymer-nanoparticle interaction in the temperature range where the polymer is thermally stable (does not degrade). The existence of an immobilized fraction in PMMA SiO₂ nanocomposites was shown on the basis of heat capacity measurements at the glass transition of the polymer. The results were verified by enthalpy relaxation experiments below the glass transition. The immobilized layer is about 2 nm thick at low filler content if agglomeration is not dominant. The thickness of the layer is similar to that found in semicrystalline polymers and independent from the shape of the nanoparticles. Nanocomposites therefore offer a unique opportunity to study the devitrification of the immobilized fraction (RAF) without interference of melting of crystals as in semicrystalline polymers. It was found that the interaction between the SiO₂ nanoparticles and the PMMA is so strong that no devitrification occurs before degradation of the polymer. No gradual increase of heat capacity or a broadening of the glass transition was found. The cooperatively rearranging regions (CRR) are either immobilized or mobile. No intermediate states are found. The results obtained for the polymer nanocomposites support the view that the reason for the restricted mobility must disappear before the RAF can devitrify. For semicrystalline polymers this means that rigid crystals must melt before the RAF can relax.