聚(2,5-苯并(口恶)唑)/多壁碳纳米管复合材料的制备与性能

采用强氧化性酸处理多壁碳纳米管(MWNTs),形成功能化的多壁碳纳米管(MWNTs-COOH)。用傅里叶红外光谱(FT-IR)对处理前后MWNTs的表面官能团进行了分析,并利用原位聚合法成功制备了聚(2,5-苯并噁唑)(ABPBO)/MWNTs-COOH纳米复合材料。结果表明:碳纳米管经过酸处理后,表面含有较多羰基和羟基极性官能团,在ABPBO基体中分散均匀;复合材料保持了ABPBO的优异耐高温性能,其力学性能和光物理性能也得到了很大的提高。     

聚(2,5-苯并噁唑)/多壁碳纳米管复合材料的制备与性能

采用强氧化性酸处理多壁碳纳米管(MWNTs),形成功能化的多壁碳纳米管(MWNTs-COOH)。用傅里叶红外光谱(FT-IR)对处理前后MWNTs的表面官能团进行了分析,并利用原位聚合法成功制备了聚(2,5-苯并噁唑)(ABPBO)/MWNTs-COOH纳米复合材料。结果表明:碳纳米管经过酸处理后,表面含有较多羰基和羟基极性官能团,在ABPBO基体中分散均匀;复合材料保持了ABPBO的优异耐高温性能,其力学性能和光物理性能也得到了很大的提高。     

受限空间内聚苯乙烯微粒的制备

以(N,N-二甲氨基-4-吡啶)五氰合铁(II)封端的聚氧丙烯聚氧乙烯共聚物(EPE-Fe)与苯乙烯在水中自组装形成纳米体系(EPE-Fe-St), 在纳米尺度受限空间内进行了苯乙烯自由基聚合, 制备了聚苯乙烯微球(EPE-Fe-PS). 用Fe³⁺对自组装体系的纳米球壳进行固化后形成Fe-EPE-Fe-St 体系, 聚合后也制备了聚苯乙烯微球(Fe-EPE-Fe-PS). 研究结果表明,制备了粒径为60～200 nm 的不同粒径单分散聚苯乙烯微球, 聚合温度对纳米Fe-EPE-Fe-St 体系粒径影响较小, 而对EPE-Fe-St 体系较大. 在受限空间内苯乙烯的自由基聚合可得到数均分子量超过70 万的聚苯乙烯; 自组装体系中引发剂量增多使聚苯乙烯分子量下降, 聚合温度上升也使分子量下降, 而增加自组装的EPE-Fe 用量可增加聚苯乙烯的分子量. 两种受限条件下的聚苯乙烯微球的玻璃化转变温度(T_g)在90～135 ℃之间, 纳米反应器壳层的硬化提高了聚苯乙烯微球的T_g.     

三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

聚合酞菁铁/多壁碳纳米管复合材料的制备及氧还原催化性能

采用高效、 便捷的微波合成法制备了4种不同结构的聚合酞菁铁/多壁碳纳米管(Poly-FePc/MWCNTs)复合材料并进行了表征. 结果表明, 聚合酞菁铁均匀地包裹在多壁碳纳米管上. 利用线性扫描电位法(LSV)和电化学阻抗法(EIS)对材料的氧还原催化活性进行了研究, 发现FePPc/MWCNTs复合材料具有最好的氧还原催化活性. 采用X射线光电子能谱(XPS)和X射线吸收精细结构光谱(XAFS)研究了Poly-FePc/MWCNTs复合材料中酞菁铁结构变化与氧还原催化性能的相关性. 结果表明, FePPc/MWCNTs复合材料中Fe-N₄接近平面结构, 聚合酞菁铁能够更好地与MWCNTs产生协同作用, 从而加速氧还原过程中电子的转移, 提高氧还原活性.     

超声辐照原位乳液聚合制备聚苯乙烯包覆碳纳米管复合材料的结构与性能

采用超声辐照原位乳液聚合方法制备了聚苯乙烯(PS)包覆多壁碳纳米管(MWNTs)复合材料. 用TEM, FTIR, UV, XPS, GPC和TGA研究了复合材料的结构和性能. 结果表明, MWNTs对苯乙烯聚合过程具有抑制作用, 聚苯乙烯包覆MWNTs, 两者之间有较强的相互作用, 使复合材料的热性能得到改善, 起始分解温度从388 ℃提高到422 ℃.     

聚乙酰苯胺修饰碳纳米管载铂催化剂对甲醇电催化氧化

以原位化学聚合的聚乙酰苯胺/多壁碳纳米管(PAANI-MWCNTs)复合纳米材料作为载体,采用硼氢化钠还原法将Pt纳米粒子担载到PAANI-MWCNTs复合纳米材料表面,制备了Pt/PAANI-MWCNTs复合纳米催化剂.样品的结构和形貌用紫外-可见(UV-Vis)光谱、拉曼光谱、扫描电镜(SEM)、透射电镜(TEM)和X射线衍射(XRD)进行了表征.结果表明,聚乙酰苯胺与碳纳米管之间存在较强的π-π相互作用,使其能牢固地吸附于多壁碳纳米管表面,对碳纳米管的结构完整性和导电性有一定的改善作用.同时,金属Pt纳米颗粒较为均匀地分散在PAANI-MWCNTs表面,粒径分布范围较窄.采用循环伏安法和计时电流法在酸性溶液中研究了Pt/PAANI-MWCNTs催化剂对甲醇的电催化氧化活性,结果表明Pt/PAANI-MWCNTs复合纳米催化剂比用混酸处理的碳纳米管载铂催化剂对甲醇呈现出更高的电催化氧化活性和更好的抗中毒能力及稳定性.     

基于Diels-Alder反应与原子转移自由基聚合制备核壳型碳纳米管-笼型倍半硅氧烷杂化材料

通过糠醇与溴代异丁酰溴的酯化反应制备了溴代异丁酸呋喃甲酯,其与多壁碳纳米管(MWNT)发生Diels-Alder环加成反应得到了原子转移自由基聚合(ATRP)的引发剂(MWNT-Br),MWNT-Br通过ATRP反应引发了八丙烯酸酯基笼型倍半硅氧烷(POSS)的聚合,从而实现了POSS对多壁碳纳米管的包覆,通过对MWNT-Br中溴代异丁酸呋喃甲酯接枝量的控制,包覆POSS层的厚度可以从5 nm、10 nm到15 nm精确调节.     

基于纳米银/多壁碳纳米管修饰电极的电化学法测定磺胺甲唑

以表面处理多壁碳纳米管(MWCNTs)和硝酸银为原料,利用硼氢化钠还原法制备了纳米银/多壁碳纳米管复合材料(AgNPs/MWCNTs),并通过紫外-可见吸收光谱、红外光谱、拉曼光谱和X射线衍射进行表征。采用滴涂法将该纳米复合材料修饰至玻碳电极表面,得到纳米银/多壁碳纳米管修饰电极(AgNPs/MWCNTs/GCE)。以AgNPs/MWCNTs/GCE为工作电极,研究了缓冲溶液、pH值、支持电解质和扫描速度对磺胺甲■唑(SMZ)电化学反应活性的影响。结果表明,与多壁碳纳米管、纳米银单独修饰电极相比,该纳米复合材料修饰电极对SMZ显示了更高的电催化活性。优化条件下,SMZ浓度在3.0×10~(-7)～5.0×10~(-5) mol/L范围内与峰电流呈线性关系,检出限(S/N=3)为6.4×10~(-8) mol/L。该方法操作简单、快速,可用于河水样品中SMZ的检测。     

Fe3O4表面原位引发可控/“活性”聚合制备磁性聚苯乙烯纳米粒子

采用化学共沉淀方法合成了Fe3O4纳米粒子, 用3-甲基丙烯酰氧基丙基三甲氧基硅烷(3-MPS)对其进行表面接枝修饰, 然后以苯乙烯(St)为单体, 过氧化苯甲酰(BPO)为引发剂, 4-羟基-2,2,6,6-四甲基哌啶-1-氧化物自由基(HTEMPO·)为稳定自由基介质, 采用可控/“活性”自由基聚合技术在修饰后的Fe3O4纳米粒子表面原位引发聚合, 制备了粒径小、分布窄、磁含量高的磁性聚苯乙烯（PS）纳米粒子. X射线衍射(XRD)研究表明, 所合成的Fe3O4粒子为尖晶石结构. 凝胶渗透色谱(GPC)分析表明, 聚苯乙烯的分子量与反应时间呈较好的线性关系. 透射电镜(TEM)观察表明, 所制备的磁性聚苯乙烯纳米粒子的粒径在20-30 nm之间. 热重(TG)分析得到磁性聚苯乙烯纳米粒子的磁含量为62.6%. 振动样品磁强计(VSM)测试结果表明, 磁性聚苯乙烯纳米粒子的比饱和磁化强度为31.7 emu·g-1, 呈现单磁畴结构.     

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.     

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.     

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.     

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.