Inverse relaxation-model and relation to recovery internal friction

Inverse relaxation is studied for hard elastic polypropylene (HEPP), rubber and non-elastic polypropylene. The results show that contractive stress, stress, and internal friction are three essential factors related to the phenomenon. A three-element model in which each element has a definite meaning is proposed to describe this phenomenon. The results also show that, in the first cyclic deformation, relaxation time increases with the increase of recovery for all the materials, which indicates that recovery viscosity increases with the increase of recovery, but the stress rising amplitude (SRA) of inverse relaxation has a maximum in the recovery range. Analysis indicates that SRA equals recovery internal friction (RIF) for ideal material in which stress is solely a function of strain, independent of paths, and approximately equals RIF for non-ideal material at a given strain. From this principle it is found that the order of the work counteracted by RIF for the four materials is the same as that of their second hysteresis loop, and the RIF of HEPP has a sudden increase at the later recovery range.     

A highly stereoselective synthesis of the C10–C31 (BCDEF ring) portion of pinnatoxin A

An efficient, highly stereoselective synthesis of the C10–C31 (BCDEF ring) portion of pinnatoxin A has been achieved utilizing tandem double hemiketal formation/intramolecular hetero-Michael addition to construct the 6,5,6-dispiroketal (BCD ring) system and subsequent intramolecular ketalization to form the 5,6-bicycloketal (EF ring) system as key steps.     

Time-resolved fluorescence analysis of the mobile flavin cofactor in p -hydroxybenzoate hydroxylase

Conformational heterogeneity of the FAD cofactor in p-hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate (analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations; the ‘in’ conformation with the isoalloxazine ring located in the active site, and the ‘out’ conformation with the isoalloxazine ring disposed towards the protein surface. Fluorescence-lifetime analysis of these complexes revealed similar lifetime distributions for the ‘in’ and ‘out’ conformations. The reason for this is twofold. First, the active site of PHBH contains various potential fluorescence-quenching sites close to the flavin. Fluorescence analysis of uncomplexed PHBH Y222V and Y222A showed that Tyr222 is responsible for picosecond fluorescence quenching free enzyme. In addition, other potential quenching sites, including a tryptophan and two tyrosines involved in substrate binding, are located nearby. Since the shortest distance between these quenching sites and the isoalloxazine ring differs only little on average, these aromatic residues are likely to contribute to fluorescence quenching. Second, the effect of flavin conformation on the fluorescence lifetime distribution is blurred by binding of the aromatic substrates: saturation with aromatic substrates induces highly efficient fluorescence quenching. The flavin conformation is therefore only reflected in the small relative contributions of the longer lifetimes.     

Conformational studies of soluble and immobilized frog epidermis tyrosinase by fluorescence

Fluorescence spectra and soluble quenching of intrinsic protein fluorescence were used as indexes of conformational changes suffered by frog epidermis tyrosinase. The activation process and the immobilization of the enzyme involving either free amino groups or its carbohydrate moiety were studied. The conformational changes resulting from denaturation of each one of the protein derivatives, as well as the effect of active center copper extraction, were followed by fluorescence studies. The results showed that: (a) both activation and immobilization were accompanied by conformational changes of the protein leading to more unfolded states; (b) neither enzyme nor immobilized enzyme were fully unfolded upon denaturation although enzymic activity was lost; (c) the enzyme immobilized through its carbohydrate moiety was more unfolded upon denaturation than the enzyme immobilized through amino groups, thus pointing to a higher conformational stabilization in the last situation; and (d), that tryptophyl residues moved to a localization near the active site upon activation.     

原子荧光光谱法测定砷过程中还原反应条件的优化

自然界中砷和砷的化合物一般可通过水、大气和食物等途径进入人体,危害人体健康,原子荧光光谱法测定砷含量被广泛应用。为准确测定样品中砷的含量,以原子荧光光谱法(AFS)测定土壤中总砷含量为例,重点研究高价态砷(Ⅴ)还原为低价态砷(Ⅲ)的实验条件,采用正交实验进行条件优化,建立适合的实验方法。通过设计L9(34)正交实验,高价态砷的还原反应与四个因素有关,即与反应温度、反应时间、盐酸加入量和硫脲的用量呈一定的正相关,结果表明,四个因素中硫脲用量的影响最为显著,其次是盐酸加入量、反应时间和反应温度。通过对四个因素的多水平检验,优化后的实验条件为：硫脲用量2.0 mL、盐酸加入量10%、反应时间20 min、温度20～35 ℃(即普通室温)。采用土壤标准物质验证优化后条件的可行性,得出砷的测定值在标准值范围内,RSD在2.2%～4.2%,精密度和准确性均满足质控要求。优化后的实验条件使得操作简便易行,提高了工作效率。     

X射线荧光光谱(XRF)法测定绿泥石中镁、铝、硅、磷、钾、钙、钛、铁元素含量

建立了X射线荧光光谱法测定绿泥石中镁、铝、硅、磷、钾、钙、钛、铁元素含量的快速分析方法。以标准物质及标准物质与基准试剂氧化镁、氧化钙人工混合配制标样的方法建立标准工作曲线,重点讨论了熔剂和脱模剂的选取。最佳熔样条件：采用8.0g四硼酸锂和偏硼酸锂混合熔剂(质量比67: 33)+0.8g样品并添加溴化锂作为脱模剂,熔样温度1100℃,熔样时间10min。该方法相对标准偏差(n=12)均小于5.57%,绿泥石样品测定结果与化学法一致,硅酸盐标准物质测定结果均满足不确定度要求。     

粉末压片-X荧光光谱法测定过磷酸钙中硫含量

硫是过磷酸钙中重要营养指标之一,为准确快速测定过磷酸钙中硫的含量,试验采用粉末压片-X荧光光谱法,将过磷酸钙试样充分干燥后研磨至粒度小于74 μm,采用硼酸镶边,在压力18 Mpa条件下保压30 s,制成样片。通过在过磷酸钙样品中添加不同质量的纯物质硫酸钙（质量分数范围1.52 %～17.21 %）,经过专用混匀设备混合均匀后,与试样压片相同条件下压制标准样片,作为过磷酸钙中硫的标准样品,建立硫标准曲线,曲线线性相关系数R2为0.9995,采用经验系数法校正干扰,建立了粉末压片-波长色散X射线荧光光谱法测定过磷酸钙中硫含量的方法, 方法检出限为0.002 %。对3个不同硫含量的过磷酸钙样品采用本实验方法重复测量7次,RSD在1.4 %~3.1 %,方法精密度性好,同时用高温燃烧红外光谱法和电感耦合等离子发射光谱法对比,三者测量结果相对极差小于2.0 %,测量结果无显著性差异。此方法不需要对样品进行熔融或溶解,样品制备简单,数据准确度和稳定性好,分析效率高,适合大批量样品中硫的测定。     

锗元素测定方法综述

锗在国防工业、航空航天和通信等领域中的战略性,锗含量的测定对于保证材料质量和满足国际标准至关重要。本文综述了锗含量测定方法的多种技术,包括分光光度法、原子荧光光谱法、原子吸收光谱法、电感耦合等离子体原子发射光谱法、电感耦合等离子体质谱法以及滴定法。在每个检测方法的介绍中,详细探讨了方法的原理、前处理步骤以及应用范围,并分别总结了各个方法的优势和不足。最后,强调了锗含量测定方法的意义,特别是在满足出口监管和促进科学研究方面的作用。同时对锗元素的测定方法进行了展望,为未来的发展提供了参考方向。     

Ultrasound-Assisted Synthesis of Fluorescent Azatetracyclic Derivatives: An Energy-Efficient Approach

We report here an energy-efficient and straight synthesis of two new classes of derivatized fluorescent azatetracycles under ultrasound (US) irradiation. A first class of azatetracyclic compounds was synthesized by heterogeneous catalytic bromination of the α-keto substituent attached to the pyrrole moiety of the tetracyclic cycloadducts, while for the second, one class was synthesized by nucleophilic substitution of the bromide with the azide group. Comparative with conventional thermal heating (TH) under US irradiation, both types of reactions occur with substantially higher yields, shortened reaction time (from days to hours), lesser energy consumed, easier workup of the reaction, and smaller amounts of solvent required (at least three to five-fold less compared to TH), which make these reactions to be considered as energy efficient. The derivatized azatetracycle are blue emitters with λmax of fluorescence around 430–445 nm. A certain influence of the azatetracycle substituents concerning absorption and fluorescent properties was observed. Compounds anchored with a bulky azide group have shown decreased fluorescence intensity compared with corresponding bromides.     

Light-Responsive Hexagonal Assemblies of Triangular Azo Dyes

The rational design of small building block molecules and understanding their molecular assemblies are of fundamental importance in creating new stimuli-responsive organic architectures with desired shapes and functions. Based on the experimental results of light-induced conformational changes of four types of triangular azo dyes with different terminal functional groups, as well as absorption and fluorescence characteristics associated with their molecular assemblies, we report that aggregation-active emission enhancement (AIEE)-active compound (1) substituted with sterically crowded tert-butyl (t-Bu) groups showed approximately 35% light-induced molecular switching and had a strong tendency to assemble into highly stable hexagonal structures with AIEE characteristics. Their sizes were regulated from nanometer-scale hexagonal rods to micrometer-scale sticks depending on the concentration. This is in contrast to other triangular compounds with bromo (Br) and triphenylamine (TPA) substituents, which exhibited no photoisomerization and tended to form flexible fibrous structures. Moreover, non-contact exposure of the fluorescent hexagonal nanorods to ultraviolet (UV) light led to a dramatic hexagonal-to-amorphous structure transition. The resulting remarkable variations, such as in the contrast of microscopic images and fluorescence characteristics, were confirmed by various microscopic and spectroscopic measurements.