煤沥青基中间相炭微球的电化学性能与微观结构

将煤焦油沥青基中间相炭微球(MCMB)在一定的工艺条件和不同最高热处理温度(HTT_max)下进行高温热处理,利用XRD和Raman光谱分析了不同HTT_max下MCMB试样的微观结构.借助恒电流充放电和粉末微电极循环伏安法考察了试样的宏观电化学性能,探讨了中间相炭微球宏观电化学性能与其微观结构间的联系.研究表明,随着HTT_max的升高,中间相炭微球从低温热解炭的结构特征向石墨晶体结构转变,材料的电化学贮锂机制相应地也从微孔贮锂向石墨层间嵌锂机制转变.MCMB特殊的弧状碳层走向使得石墨微晶的L_a值未能随HTT_max的升高而大幅度增长,这是高温热处理MCMB的宏观电化学性能随HTT_max的升高而不断提高的内在原因.     

SOCl2／SnCl4—DMSO／n—Bu4NCl引发体系苯乙烯活性阳离子聚合反应的研究

研究表明，ＳＯＣｌ２／ＳｎＣｌ４引发体系的苯乙烯聚合反应很快，但所得聚合产物的分子量分布宽（Ｍｗ／Ｍｎ＝４．３７），且其ＧＰＣ曲线呈多重峰；单独加入季铵盐（ｎ－Ｂｕ４ＮＣｌ）或二甲基亚砜（ＤＭＳＯ）可使聚合产物分子量分布明显变窄，并随浓度的增加而加强，但程度有限，不显示活性聚合特征；ＤＭＳＯ和ｎ－Ｂｕ４ＮＣｌ同时加入，表现出协同效应，不仅能保持较高的聚合反应活性，而且产物分子量分布很窄（Ｍｗ／Ｍｎ＝１．２７），分子量随单体转化率增加而增加，且线性关系良好，聚合物链数只与引发剂初始浓度相关，显示活性聚合特征。     

胶束体系中光敏聚合的研究 Ⅶ．微泡水溶液体系中光聚合的研究

研究了在双十六烷基二甲基溴化铵（ＤＣＤＡＢ）形成的微泡溶液中，二苯酮（ＢＰ）／三乙胺（ＴＥＡ）体系的光化学初级反应和引发ＭＭＡ光聚合反应．动力学实验结果表明，ＤＣＤＡＢ微泡对聚合反应有显著的催化作用，使聚合速度提高近４倍左右，其效果和离子型胶束的催化作用结果相近．由ＤＣＤＡＢ微泡中光聚合得到的产物ＰＭＭＡ，具有较高的结构规整性，它的间同和全同结构可达７０％左右．     

新型FCC催化剂的制备与性能

研究了高岭土型流化催化裂化催化剂的制备与性能，粒度分布中粒么μｍ左右的细高岭土，经浆化和喷雾成型制在４０－８０目的母体微球，部分微球在高温下焙烧使生高岭土通过高于特征温度焙烧转化为ＣＭＡ，另一部分在较低温度下焙烧使其转化为偏高岭ＣＭＢ。ＣＭＡ和ＣＭＢ混合后与硅酸钠等反应２０－３０ｈ，使混合球上发生晶化，生成２５％以上的ＮａＹ分子筛。     

CuX／bpy催化体系中甲基丙烯酸甲酯的原子转移自由基聚合

讨论了以α－溴代丙酸乙酯（ＥＰＮ－Ｂｒ）为引发剂、卤化亚铜（ＣｕＸ）／联二吡啶（ｂｐｙ）为催化剂，８０℃下，甲基丙烯酸甲酯（ＭＭＡ）地不同溶剂中的原子转移自由基聚合（ＡＴＲＰ）反应。通过对催化剂ＣｕＢｒ或ＣｕＣｌ及几种溶剂的考察，发现在８０℃下ＥＰＮ－Ｂｒ／ＣｕＢｒ／ｂｐｙ能有效控制丙烯酸甲酯（ＭＡ）的本体ＡＴＲＰ反应，但并不能很好地控制ＭＭＡ在ＥＡｃ中的聚合反应为一可控聚合过程，引发效率为０．８     

季胺盐型表面活性剂与镉试剂显色反应的研究及应用

在三乙醇胺存在下，季铵盐型表面活性剂溴化十六烷基三甲铵，溴化十二烷基二甲基苄铵和溴化十六烷基吡啶分别与１－（４－硝基苯基）－３－「４－苯基偶氮）苯基」－三氮烯形成离子缔合物显色，吸收光谱红移，离子缔合物；ＮＰ－ＰＡＰＴ与ＤＤＭＢＡＢ来１：２与ＣＴＭＡＢ，ＣＰＢ均为１：３；测定了显色体系的ＣＴＭＡＢ，ＤＤＭＢＡＭ，ＣＰＢ的临界胶束浓度，符合比尔定律的范围，表观摩尔吸光系数δｍａｘ，探讨了微量ＣＴＭＡ     

铈（Ⅳ）盐引发丙烯酰胺在β－二羰基结构功能化聚苯乙烯微球上的接枝聚合研究

将乙酰丙酮（ＡｃＡｃ）、乙酰乙酸乙酯（ＡｃＡｃＥ）、苯甲酰基丙酮（ＢｚＡｃ）作为β－二羰基基团通过烷基化反应，引入到氯甲基聚苯乙烯（ＰＳｔ－ＣＨ２Ｃｌ）微球，研究了该微球在硝酸铈铵（ＣＡＮ）存在下引发丙烯酰胺（ＡＡＭ）的接枝聚合，以接技前后β－二羰基功能化聚苯乙烯微球吸水率及氮含量的变化、颗粒的增重、ＥＳＣＡ及ＦＴ－ＩＲ光谱、显微照相等方法，对接枝聚合物进行了表征，并提出了接技聚合反应的机理．     

微米级聚酯醚嵌段共聚物微球的制备及其蛋白包裹研究

聚酯 醚嵌段共聚物聚 Ｄ，Ｌ 乳酸 聚乙二醇（Ｐｏｌｙ ＤＬ ｌａｃｔｉｄｅ Ｐｏｌｙｅｔｈｙｌｅｎｅｇｌｙｃｏｌ，ＰＬＡ ＰＥＧ）采用本体聚合法在１８０℃及－９５×１０－２ＭＰａ条件下制得．光谱分析证实产物结构．采用乳液溶剂蒸发法制备ＰＬＡ ＰＥＧ微球，粒径＜５μｍ．以复合乳液技术包裹蛋白．差示扫描量热分析确证ＰＬＡ ＰＥＧ有效包裹蛋白．ＢＣＡ法检测微球蛋白含量．结果表明与均聚物ＰＬＡ比较，ＰＬＡ ＰＥＧ不仅改善了成球条件而且蛋白的包裹效率明显提高．     

AlCl_3／SbCl_3引发α－蒎烯阳离子聚合反应──引发活性种本质研究

考察了复合催化剂ＡｌＣｌ_３／ＳｂＣｌ_３的不同配制方法和质子捕捉剂２，６－二异丁基－４－甲基吡啶（ＤＴＢＭＰ）对α－蒎烯阳离子聚合反应的影响。结果表明，ＡｌＣｌ_３和ＳｂＣｌ_３加热熔融复合比简单复合的引发聚合活性更高；ＤＴＢＭＰ对该复合催化剂的聚合反应速率及其产物分子量分布均无明显影响，证明该复合催化剂形成的活性种本质上与质子Ｈ活性种不同，是新型活性种。根据２７ＡｌＮＭＲ对该体系活性种分析结果，认为引发阳离子是［Ｓｂ（Ｖ）Ｃｌ_４］，抗衡阴离子是［Ａｌ_２Ｃｌ_７］     

AlEtCl_2／t－BuCl引发α－蒎烯阳离子聚合反应研究

考察了在ＡｌＥｔＣｌ２／ｔ－ＢｕＣｌ引发体系作用下的α－蒎烯阳离子聚合行为．结果表明，ｔ－ＢｕＣｌ与ＡｌＥｔＣｌ２复合后，由于生成（ＣＨ３）Ｃ正离子而使引发活性增大．但ｔ－ＢｕＣｌ的引人对产物分子量及其分布影响不大，产物主要由二、三聚体组成．聚合过程的动力学研究表明，α－蒎烯在进行阳离子聚合时容易发生链终止反应而导致单体转化率和产物分子量较低．α－蒎烯在聚合反应的同时伴随着异构化反应，用制备ＧＰＣ分离出异构化产物，然后经１ＨＮＭＲ测定其结构．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.