热致型液晶聚合物的等温和非等温晶化动力学

利用等温和非等温方法详细研究了芳香族聚酯──热致型聚合物对，对’－联苯二甲酸二辛酯的结晶相和液晶相形成机理，并计算了相变过程中的表面自由能与温度系数，研究结果表明：从介晶相开始的结晶过程是二维异相成核、三维线性增长的，而从各向同性液相开始的液晶相形成过程则是二维异相成核二维线性增长的．对两个晶化过程的表面自由能的研究表明，该聚合物液晶相形成过程的相转变表面自由能比结晶过程小得多，预示了它将具有更大的晶化速率．研究还发现，该聚合物的液晶相形成过程具有比结晶过程大得多的温度敏感性．     

N,N,N′-Trialkyl-1,8-diaminonaphthalenes: convenient method of preparation from protonated proton sponges and the first X-ray information

A simple procedure for the synthesis of N,N,N′-trialkyl-1,8-diaminonaphthalenes is described. It consists in partial demethylation (dealkylation) of commercially available proton sponge [1,8-bis(dimethylamino)naphthalene] and some of its derivatives at heating with HBr-KI-DMF system. Limitation, scope and a possible mechanistic pathway for the reaction are discussed. For isomeric 8-dimethylamino-1-methylamino- and 1-dimethylamino-8-methylamino-4-nitronaphthalenes, X-ray measurements have been conducted. The first examples of complete realkylation reactions in the naphthalene proton sponges are reported.     

Synthesis and characterization of Cu,Ni and Zn binding capability of some amino- and imidazole hydroxamic acids: Effects of substitution of side chain amino-N for imidazole-N or hydroxamic-N-H for -N-CH3 on metal complexation

Solution equilibrium studies on Cu(II)-, Ni(II)- and Zn(II)-N-Me-β-Alaninehydroxamic acid (N-Me-β-Alaha), -N-Me-α-alaninehydroxamic acid (N-Me-α-Alaha), -Imidazole-4-carbohydroxamic acid (Im-4-Cha), -N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha) and -Imidazole-4-acetohydroxamic acid (Im-4-Aha) systems have been performed by pH-potentiometry, UV–Vis spectrophotometry, EPR, CD, ESI-MS and ¹H NMR methods. According to the results: (i) the amino-N atoms are more basic in N-Me-α-Alaha and N-Me-β-Alaha than the hydroxamate function, but the trend is just the opposite between the imidazole-N(3) and hydroxamate. (ii) The metal ion anchor is always the hydroxamate part in the amino acid derivatives, while it is always the imidazole-N(3) in the studied imidazolehydroxamic acids. (iii) The three studied N-Me derivatives do not form metallacrowns. Only hydroxamate type chelate is formed with N-Me-β-Alaha, but with N-Me-α-Alaha a new type of coordination mode (via amino-N and hydroxamate-O) also exists. N-Me-Im-4-Cha also forms a dinuclear complex, [M₂L₃], with Cu(II) and Ni(II) (but not with Zn(II)). In this complex, one of the three ligands might bridge the two metal ions (five-membered hydroxamate-(O,O) plus five-membered (N_im, O_carb) bridging bis-chelating mode), while each of the additional two ligands binds to one metal. (iv) The two studied N–H derivatives, having dissociable proton on the hydroxamic-N, are able to form metallacrown species. A pentanuclear complex, [M₅L₄H₋₄], is exclusively formed above pH 4 between Cu(II) and Im-4-Aha. Interestingly, this 12-metallacrown-4 type complex, although together with various mononuclear binding isomers, appears also with Ni(II) and Zn(II). Unfortunately, the complexes of Im-4-Cha are not soluble in water at physiological pH at all.     

苯并三氮唑及其羧酸酯衍生物对铜缓蚀机理的分子动力学模拟研究

用分子动力学(MD)方法, 模拟计算了5种铜缓蚀剂[苯并三氮唑(BTA)、苯并三氮唑-5-羧酸甲酯(MBTC)、苯并三氮唑-5-羧酸丁酯(BBTC)、苯并三氮唑-5-羧酸己酯(HBTC)、苯并三氮唑-5-羧酸辛酯(OBTC)]与Cu₂O晶体的相互作用. 结果发现, 中性条件下缓蚀剂分子与Cu₂O晶体的结合能均大于酸性条件下的数值, 但两种条件下结合能的大小排序均为OBTC＞HBTC＞BBTC＞MBTC＞BTA. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供, Cu₂O晶体中的Cu原子与缓蚀剂分子中的N原子之间形成了配位键. 在与Cu₂O(001)晶面结合过程中, BTA及其衍生物分子发生了扭曲变形, 但形变能远小于体系的非键相互作用能.     

COMBINED PARTIAL OXIDATION AND CARBONDIOXIDE REFORMING OF METHANE PROCESS TO SYNTHESIS GAS

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Influence of velocity and surface temperature of alumina particles on the properties of plasma sprayed coatings

In this paper are described the main characteristics of the plasma spraying process of alumina deposits, i.e., the temperature and flow field of the plasma jets obtained with the classical spraying torches, the injection of the particles into the plasma jet, the particle surface temperature and velocities in the plasma (measured for calibrated alumina particles), and the coating generation. The measurements on the alumina particles are compared with the predictions of a mathematical model. The experimental and computed particle velocities are in rather good agreement. However, this is not the case for the particle surface temperature. Possible reasons for the discrepancy are proposed (influence of the carrier gas, thermophoretic forces, and poor penetration of the particles into the plasma core even for an injection velocity twice that of the optimal calculated one, as shown by recent measurements). Finally the correlations between the particle velocities and surface temperature, and the properties of the alumina coating (porosity, crystal structure, mechanical properties) are studied.     

2,4—二氨基—5—取代苄基嘧啶类质谱研究

报道了8个2,4-二氨基-5-取代苄基嘧啶衍生物的电子轰击质谱及碰撞活化解离和质量分析离子动能谱.该谱提供了化合物醚键及2,4-二氨基-5-取代苄基嘧啶环的主要碎裂途径,总结了一些裂解规律,将有助于这类化合物的结构推断。     

糠酸一步催化法制备四氢糠酸甲酯

以糠酸、甲醇、氢气为原料,采用连续流动固定床微反应器,Pd-Ni/γ-Al2O3为催化剂,使糠酸一步加氢甲酯化生成α-四氢糠酸甲酯.研究了反应的温度,压力,气、液体流速,进料流量等因素对催化反应的影响.结果表明:在1.5MPa,250℃,氢气空速3300 h-1,液体空速3.0 h-1(氢油比为50)时,糠酸转化率为96.6%,四氢糠酸甲酯的选择性97.2.0%,产率94.0%.催化剂稳定性较好,连续运转280小时后未见活性下降.该反应体系活性高,选择性好,反应压力低,催化剂性能稳定,操作简单,产物易分离.     

化学与社会:跨学科视角下的通识课教学新探索

从通识教育的时代要求和化学的学科地位出发，首先讨论了在化学类通识课程建设中引入跨学科视角的意义和可操作性。随后以通识课"化学与社会"的建设为例，系统地分享了引入跨学科视角后的课程设计理念和内容框架建设，通过课堂实施方案的论述和特色实例的分享总结了课程实施经验，并以学生访谈资料分析讨论了课程取得的效果和需要进一步完善的方向。以期为跨学科理念在化学教育教学实践中的转化和落地开拓思路、提供经验。     

SSCH3光解离的多参考理论计算

摘要运用多参考微扰理论(Multireference MΦller-Plesset theory)计算了SSCH3垂直激发能及其S-C与S-S两种断键方式的绝热(Adiabatic)与非绝热(Diabatic)的基态和激发态势能曲线, 研究了在193nm激光作用下SSCH3的光解离过程, 理论计算值与实验值相符.