秩为4的Jacobian的性质与应用

描述了秩为4的一阶及二阶Jacobian的性质和运算规则,探讨了运用Mathematica软件及秩为4的Jacobian研究二组分单相系统的热力学一、二阶偏微商的方法。     

作者来信照登

编辑先生:我在贵刊2009年,11期,987页到992页发表的文章"秩为3的Jacobian的性质和它在热力学中的应用"最近我重读了一下,在988页倒19行处,"6种不同Maxwell关系式,它们是…:"后,文中只列出     

三维荧光二阶校正法用于未知混合物中苯酚含量的测定

将三维荧光光谱技术与秩消失因子分析、广义秩消失因子分析和交替三线性分解3种二阶校正方法相结合,建立了测定未知混合物中苯酚含量的三维荧光二阶校正新方法。设定在激发波长240~280 nm和发射波长280~360 nm范围内测定未知混合物中苯酚的三维荧光光谱,构建三维响应数据阵,运用基于三线性分解的二阶校正算法进行解析。结果表明,当模拟样品的组分数为2时,秩消失因子分析、广义秩消失因子分析和交替三线性分解3种方法测定苯酚的预测均方根误差分别为0.33,1.18和0.15,平均回收率分别为101.6%,115.6%和101.9%;当组分数为3时,3种方法的预测均方根误差则分别为1.61,1.80和0.51,平均回收率分别为134.2%,133.9%和107.1%;将其分别应用于实际样品中苯酚的测定,结果满意,且交替三线性分解法的测定结果优于秩消失因子分析法和广义秩消失因子分析法。     

推证热力学函数偏微商方法的探讨

推证热力学函数偏微商方法的探讨高建安（南方冶金学院，赣州３４１０００）１引言热力学体系常用的八个热力学函数（Ｔ、Ｐ、Ｖ、Ｓ、Ｕ、Ｈ、Ｆ、Ｇ）间存在３３６个一级偏微商，这些偏微商在理论研究、热力学工程和教学中部有重要作用，所以不少学者对此进行了研究。热...     

用Mathematica作偏摩尔量关系式的证明

简述了溶液热力学中应用的 4维Jacobian的定义及主要运算规则 ,并给出例子说明在MathematicaNotebook界面中应用的方法     

仪器分析教学中通过实例培养学生的创新能力——电位滴定终点确定的新方法

以电位滴定终点确定新方法探讨研究为例,从5个方面介绍将创新能力培养融入基础课教学的探索。通过该研究提高了学生基础课学习热情与学习质量。首先改进了二次差值微商终点计算方法,通过Excel 计算Δ2E/ΔV-V 二次差值微商法数据表中的最高点与最低点直线线性方程 y=ax+b,令 y=0, x=-b/a即为终点。另外,研究得到了模拟滴定曲线微分法确定电位滴定终点的新方法。用Excel 对滴定曲线进行三次方程模拟即:y=ax3+bx2+cx+d,二次微分后得到: d2y/dx2=6ax+2b, 当d2y/dx2=0,对应的x=-b/3a处即为滴定终点。2     

热力学量变换的教学研究

介绍了基于热力学偏微商关系的变量变换方法,讨论了在物理化学教学中的必要性及基本要求。     

椭球情况的换置

本文将Bjerhammar换置推广到顾及椭球扁率一级效应的情况,以便适应获得高精度计算结果的特殊目的。为了实现这一推广,遵循如下途径:(a)导出含椭球扁率效应的新的Poisson积分;(b)求解径向微商边界条件的所谓简单的椭球Robin问题;(c)通过从法向微商到径向微商的边界条件交换,借助于简单Robin问题的解,导出一般的椭球Robin问题的解案。最后,将广义的Poisson积分应用到正则调和函数r△g,将一般的Robin问题的解应用到椭球情况下的线性化Molodensky问题,并将两者联合,便得到所求的椭球情况的换置。很明显,若设扁率为零,本文得到的换置则蜕化为传统的换置。     

热力学函数偏微商的求导规则

热力学函数偏微商的求导规则吴金添，苏文煅（厦门大学化学系，３１６００５）热力学函数偏微商关系式具有实际应用意义，其求导演证经常会由于函数间关系复杂而存在一些麻烦，特别是关于独立变量的变换，若无一定经验，更是一个难分难解的问题。在这方面，虽已有一些报道...     

动力学体系二维数据的秩分析及其应用

详细论证了动力学体系中存在的多种共线性情况,以及在此情况下二维数据阵的秩与独立反应数及组分数的关系.分析了通过增秩这一方式来判断体系组分数的条件.讨论了反应间存在物质交换对数据阵秩的影响.建立起一套通过秩分析判断未知动力学体系中存在的反应组分数、独立反应数以及可能反应机理的方法.将秩分析技术应用到聚苯胺与质子酸反应,初步分析了该体系存在的多种吸光性结构及结构变化.确定了[H＋]=0.01～0.1 mol•L－1范围内,聚苯胺与质子酸反应存在一个三结构两步互变过程.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.