不同形貌纳米氧化锌的水热法合成

以氯化锌为锌源,以氢氧化钠为碱源,采用水热法合成了不同形貌的纳米氧化锌;探讨了晶化时间、晶化温度、表面活性剂十六烷基三甲基溴化铵(CTAB)对纳米ZnO形貌的影响.结果表明:不添加CTAB时,在120℃下反应24h得到的纳米氧化锌为颗粒状,而在160℃下反应24h得到的纳米氧化锌为片状.当添加CTAB后,在120℃可得到片状氧化锌,而在160℃可得到颗粒状氧化锌.     

表面活性剂种类对纳米氧化锌形貌的影响

利用简单的水热法,以Zn(Ac)2.2H2O为锌源,通过调整表面活性剂的种类及碱源,制备了一系列不同形貌的纳米结构氧化锌;利用场发射扫描电子显微镜和X射线粉末衍射仪分析了产物的形貌和晶体结构,并探讨了多种表面活性剂和醋酸钠碱源对氧化锌纳米结构的影响.结果表明,以NaOH作为碱源时,在不添加任何表面活性剂的情况下,产物的形貌结构与氢氧化钠的加入量有关,当n(Zn2+)∶n(OH-)为1∶2.5、1∶10及1∶20时,分别得到片状、棒状及海胆状纳米结构的氧化锌;产物均为六方相氧化锌.     

ZnO纳米片/微棒复合体的制备、结构及光学性能

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,以氯化锌和氢氧化钠为原料,在低温水热条件下制备出具有纳米片状接枝结构的ZnO微棒。通过扫描电镜(SEM)、X射线衍射(XRD)、透射电镜(TEM)、光致发光(PL)和拉曼光谱(Raman)对产物的形貌、晶体结构和光学性能进行了表征。结果表明,表面活性剂CTAB对产物最终形貌的形成具有重要作用;微棒表面所接枝的薄片为多晶结构;产物光致发光峰是较少见的弱蓝光发射与强红光发射;同时对这种ZnO微棒的生长机理进行了探讨。     

ZnO纳米环的可控合成

以六次甲基四胺(Hexamethylenetetramine, C6H12N4)和水合硝酸锌[Zn(NO3)2·2H2O]为原料, 表面活性剂聚丙烯酰胺-氯化二烯丙基二甲基铵[poly(acrylamide-co-diallyldimethylammonium chloride, 缩写为PAM-CTAC]为形貌控制剂, 采用液相沉淀法合成了ZnO纳米环. 产物的结构与形貌经X射线粉末衍射(XRD)和扫描电子显微镜(SEM)表征. 研究了不同实验条件(如表面活性剂的浓度、反应物浓度、反应温度和反应时间等)对产物形貌与尺寸的影响. 讨论了PAM-CTAC作用下ZnO纳米环可能的形成机理. 结果表明, 合成产物为六方Wurtzite型结构的ZnO纳米环, 环内径约为220 nm, 壁厚约为70 nm. 反应物浓度、反应温度对ZnO纳米环的形成以及纳米环的尺寸都有一定的影响, 但起关键作用的是PAM-CTAC. 通过改变PAM-CTAC的浓度, 能有效地实现ZnO纳米环的可控合成. 室温荧光光谱显示, ZnO纳米环的紫外发射峰具有较窄的半高宽(FWHM)(约7 nm), 表明合成产物具有较窄的尺寸分布.     

二元阴、 阳离子表面活性剂调控合成不同形貌的介孔二氧化硅

经过简单的水热处理, 以二元阴、 阳离子表面活性剂[十六烷基三甲基溴化铵(CTAB)和十二烷基磺酸钠(SDS)分别作为阳离子表面活性剂和阴离子表面活性剂]为模板剂合成了不同形貌的介孔二氧化硅. 通过调控2种表面活性剂摩尔分数R(R=n(SDS)/[n(SDS)+n(CTAB)]), 合成了多种形貌的介孔二氧化硅. 对合成的不同形貌样品通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线粉末衍射仪(XRD) 及比表面和孔隙分析仪进行了表征. 结果表明, 随着R值从0.01变化到0.50, 介孔二氧化硅的形貌经历了一系列规律性的变化, 出现了二维六方、 层状相和反相堆积的形貌: 在R=0.01~0.18之间, 主要产物为六方相棒状结构, 且长径比随着R值增大而增大; 在R=0.20~0.28之间主要得到空心泡状结构且具有明显的演变过程; 在R=0.32~0.40之间发生了多层囊泡到单层囊泡的结构转变; 当R值超过一定范围时会产生反相堆积的形貌. 分析认为, SDS在加入过程中通过影响堆积参数g影响胶束的形貌变化, 调控了不同形貌介孔二氧化硅的合成. 各阶段产物形貌和R值的变化有直接关系, 可通过改变R值来合成特定形貌的产物.     

十六烷基三甲基溴化铵辅助作用下球形、蠕虫状和网状Pd纳米粒子的制备与表征

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,NaBH4为还原剂,通过调节水相体系中CTAB和NaBH4浓度,合成了一系列不同形貌的Pd纳米粒子,合成过程简便易行且环境友好.结果表明,随着CTAB浓度的增加,Pd粒子形貌由纳米微球逐渐向纳米线网络形态转变.CTAB浓度和NaBH4浓度是决定Pd粒子形貌的两个重要因素.     

氧化铜纳米片的水热合成与表征

利用水热法一步制备了形貌均一的氧化铜纳米片,借助场发射扫描电子显微镜、X射线粉末衍射仪和透射电子显微镜分析了产物的形貌和晶体结构;并研究了反应物浓度及表面活性剂等因素对氧化铜纳米结构的影响.结果表明,以氢氧化钠作为碱源时,在不添加任何表面活性剂的情况下,随着氢氧化钠浓度的升高,纳米片的尺寸减小、厚度增大;此外,通过添加不同的表面活性剂可以得到不同形貌的氧化铜纳米结构.     

溶胶凝胶辅助水热可控合成ZnO不同形貌分级结构光催化剂

以Zn(NO3)2·6H2O、柠檬酸和Na OH为原料,采用溶胶凝胶(sol-gel)辅助水热法,仅通过改变水热时间,就可得到片花、棒花及梭状3种不同形貌ZnO分级结构。利用XRD、SEM、UV-Vis DRS、光致发光光谱(PL)和氮低温吸附-脱附等手段对合成的ZnO样品进行了表征。推测了合成条件下不同形貌ZnO分级结构形成的机理。以活性翠兰(KGL)为模拟印染废水,考察了其光催化活性。结果表明,虽然所合成的不同形貌的ZnO样品在光照120 min后均能使KGL降解78%以上,但其中水热4 h得到的片花状ZnO光催化性能最好,可降解99%的KGL,这与其片花状的形貌、较大的比表面积、较多的表面氧缺陷和极性面有关。     

表面活性剂对导电聚吡咯性能的影响

采用十六烷基溴化铵（CTAB）、十二苯磺酸（DBSA）、十二烷基硫酸钠（SDS）3种表面活性刘为软模板,过硫酸铵为氧化剂,在0℃冰水浴条件下制备导电聚吡咯。通过改变表面活性剂的种类和用量,考察其对聚吡咯形貌和性能的影响。用FTIR、XRD、SEM等对聚吡咯材料进行表征。研究表明：表面活性剂和PPy存在一定程度上的相互协同作用,添加表面活性剂能够直接调整聚吡咯分子的形貌;掺杂DBSA、SDS可合成球状结构聚吡咯,掺杂CTAB可合成棒状结构的聚吡咯,并且当”（PPy）：n（CTAB）-5时,合成的聚吡咯导电性能最好。     

碳纳米管/ZnO纳米复合体的制备和表征

通过将不同直径的ZnO纳米颗粒与碳纳米管连接制备了碳纳米管/ZnO纳米复合体. 将团聚的ZnO纳米颗粒分散并用表面活性剂CTAB使纳米颗粒带正电. 化学氧化碳纳米管使其带负电. ZnO/CTAB微团通过碳管表面羧基与CTAB的静电作用与碳纳米管连接形成纳米复合体. 研究了复合体形成的不同实验条件, 表征了碳纳米管/ZnO纳米复合体的结构并研究了纳米复合体的光学特性. 研究表明, 与碳纳米管连接的ZnO纳米颗粒是互不连接的并保持量子点的特性. 光致发光研究表明ZnO纳米颗粒的激发在纳米复合体中有淬灭.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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 substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.