电荷转移配合物[Himi]4[Mo8O26]·16H2O的合成与表征

本文以钼酸钠和咪唑(C_3H_4N_2,imi)为原料,合成了组成为[Himi]_4[Mo_8O_(26)]·16H_2O的电荷转移配合物。通过元素分析、红外光谱、紫外光谱、热重-差热分析对其进行了初步表征。红外光谱表明,固态配合物的阴、阳离子间存在电荷转移作用;紫外光谱显示,稀水溶液中配合物完全解离,彼此无相互作用。     

电荷转移盐(C_3H_5N_2H)_3[PMo_(12)O_(40)]的合成与热分解及光致变色反应动力学

用磷钼酸与咪唑合成了一种新的杂多酸-有机电荷转移盐(C3H5N2H)3[PMo12O40]。通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究。推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×108[1-(1-α)1/3]-1(1-α)2/3exp(-40931.0/T),求得分解反应的表观活化能E=340.30kJ/mol,指前因子A=1.05×108s-1。标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学。结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10-5s-1。     

格子Boltzmann方法中三维运动边界的统一模型

格子Boltzmann方法(LBM)中边界条件的处理很复杂,在现有的边界条件处理方法中,动力学格式能够精确满足宏观边界条件,但由于要解一个不定方程,必须引入附加假设确保方程非奇异.作为动力学格式和反弹格式的一种扩展,提出一种处理三维任意速度运动边界的统一模型,其中人口速度和固体壁面速度是该模型的特殊情形.给出用于三维15速度的表达式.为了检验该模型,模拟对角顶盖驱动三维空腔流,并将结果与有限差分法计算的结果进行比较,说明所提出的统一模型是合理可行的.     

The 5-hexenyl cyclization

The cyclization of the 5-hexenyl radical to form the cyclopentylmethyl radical has been reexamined by kinetic EPR spectroscopy at temperatures between 183 and 232°K in cyclopropane solvent. The rate constant, k_c for this important radical rearrangement can be represented by where Θ = 2.3RT kcal/mol.     

On the mechanism of reaction of tert-butoxyl radicals with dialkylphosphites

It has been shown by ESR spectroscopy that the title reaction involves abstraction of hydrogen from the phosphite, since at ?10°C the reaction has a kinetic deuterium isotope effect, k_H/k_D, or ～3. The rate constant for hydrogen abstraction is c. 2 × 10⁴ M^?1 s^?1. There is no significant addition of alkoxyl radicals to the phosphite.     

Evaluation of reaction rate constants in media where they show dispersion: Hydrogen abstraction by methyl radicals in a methanol glass

Non-exponential decay of photochemically produced alkyl radicals in organic glasses is analyzed in terms of a distribution of exponential decay rate constants arising from a distribution of hydrogen transfer distances.     

螺丝钉连结的组合樑

In this paper, it is proved that the problem of composite beams jointed by bolts can be solved in terms of certain equivalent continuous beams. The equivalent beam is specified as follows: 1) It consists of supports of the original beam and equivalent supports situated at the points where bolts are used. 2) It is loaded by the given load on the original beam.Then the reactions at the bolts in the original composite beam are equal to a constant C times the reactions at various supports of the equivalent continuous beam. The constant is equal to C=(E′J′-k(EJ+E′J′))/(EJ+E′J′), where EJ and E′J′ are flexaral rigidities of the first and second parts of the composite beam respectively, and k is the distributing ratio of load on the second part.The solution of the problem is then greatly simplified.This method can be generalized for composite beams consisting of more than two parts, on which the given load is not proportionately distributed.     

Synthesis of a novel radical trapping and carbonyl group trapping anti-AGE agent: a pyridoxamine analogue for inhibiting advanced glycation (AGE) and lipoxidation (ALE) end products

[structure: see text] Pyridoxamine is known to be an effective inhibitor of both advanced glycation (AGE) and advanced lipoxidation (ALE) end products. The synthesis of a novel multifunctional AGE and ALE inhibitor, 6-dimethylaminopyridoxamine (dmaPM, 11) is described. The 6-dimethylamino substituent increases the radical trapping ability of pyridoxamine's phenolic group. Results obtained during ribose glycations show that both the new dmaPM and a known strong radical trapping agent, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox), prevent intermolecular protein cross-linking more effectively than pyridoxamine (PM).     

湖北十堰蓝色“水波纹”绿松石的谱学特征

“水波纹”绿松石是一种在外观上呈现水波纹状花纹图案的天然绿松石,产量稀少却深受消费者喜爱,前人对绿松石的研究较丰富,但对“水波纹”绿松石的研究较少。对一块基底呈浅蓝白色,条纹呈蓝绿色的“水波纹”绿松石样品用显微激光拉曼光谱仪、显微红外光谱仪、微区X射线衍射、激光剥蚀电感耦合等离子体质谱仪、扫描电镜、显微紫外-可见-近红外光谱仪等测试其各种性能。结果表明,条纹区与非条纹区的主要矿物均为绿松石;红外光谱和拉曼光谱均显示绿松石的光谱;条纹区与非条纹区的化学成分不同,条纹区Al₂O₃,SiO₂,MgO,V,Co,Ni,U及Y,Mo,Cd的含量较非条纹区含量高,而非条纹区P₂O₅,CuO,K₂O及Na₂O的含量较条纹区含量高;扫描电镜微形貌显示,条带区的晶体多为厚板状、晶体颗粒大、排列紧密,几乎不可见孔隙,非条带区的晶体多为大小不一的柱状、碎片状,杂乱排列,可见孔隙;微区X射线衍射表明条带区的结晶度较非条带区的结晶度高;显微紫外-可见-近红外光谱表明条带区与非条带区的致色离子相同,均在426和660 nm处有可见吸收峰,致色离子均为Fe3+和Cu2+。“水波纹”绿松石样品的谱学特征表明,条纹处与非条纹处的颜色差异与致色离子没有明显关系,而颜色及透明度差异与绿松石的结晶程度、致密程度有主要关系,“水波纹”绿松石中绿松石结晶度的变化表明了绿松石形成环境的不稳定性,结晶度的周期性变化表明了形成绿松石的外界环境具有周期性变化的规律,为研究绿松石的颜色成因及绿松石的成矿环境提供数据支撑。     

Cyanogenic Glycoside Analysis in American Elderberry

Cyanogenic glycosides (CNGs) are naturally occurring plant molecules (nitrogenous plant secondary metabolites) which consist of an aglycone and a sugar moiety. Hydrogen cyanide (HCN) is released from these compounds following enzymatic hydrolysis causing potential toxicity issues. The presence of CNGs in American elderberry (AE) fruit, Sambucus nigra (subsp. canadensis), is uncertain. A sensitive, reproducible and robust LC-MS/MS method was developed and optimized for accurate identification and quantification of the intact glycoside. A complimentary picrate paper test method was modified to determine the total cyanogenic potential (TCP). TCP analysis was performed using a camera-phone and UV-Vis spectrophotometry. A method validation was conducted and the developed methods were successfully applied to the assessment of TCP and quantification of intact CNGs in different tissues of AE samples. Results showed no quantifiable trace of CNGs in commercial AE juice. Levels of CNGs found in various fruit tissues of AE cultivars studied ranged from between 0.12 and 6.38 µg/g. In pressed juice samples, the concentration range measured was 0.29–2.36 µg/mL and in seeds the levels were 0.12–2.38 µg/g. TCP was highest in the stems and green berries. Concentration levels in all tissues were generally low and at a level that poses no threat to consumers of fresh and processed AE products.