聚乙烯吡咯烷酮碱性水溶液中金纳米花的简易合成

以聚乙烯吡咯烷酮(PVP)兼作保护剂和还原剂在碱性水溶液中直接还原HAuCl₄制备出了60-80 nm的三维(3D)金纳米花. 产物的透射电子显微镜(TEM)和扫描电子显微镜(SEM)图像显示, 金纳米花表面布满10-15 nm左右的纳米触角, X射线衍射(XRD)表征揭示产物为金的面心立方晶体, 选区电子衍射(SAED)花样说明金纳米花为多晶结构. 金纳米花的生长经历了三个关键步骤, 即初级纳米晶聚集成多脚状纳米粒子, 随后在合适的PVP/HAuCl₄浓度比及NaOH浓度下, 多脚状纳米粒子进一步聚集形成疏松的花状粒子, 最终经过Ostwald熟化形成致密的花状产物. 一定HAuCl₄浓度下PVP/HAuCl₄浓度比和NaOH浓度对产物的形貌影响显著, 因此通过同时调控合适的PVP/HAuCl₄浓度比和NaOH浓度, 就能得到适应各种应用需求的尺度可控和纳米触角形貌可控的金纳米花.     

纳米TiO2光催化降解聚乙二醇反应

纳米TiO2光催化降解聚乙二醇反应;纳米二氧化钛; 光催化; 聚乙二醇     

反应条件对乳液法自组装合成氧化锰纳米粒子结构、形貌和尺寸的影响

通过改变反应物物质的量比、分散相与连续相体积比、反应体系温度和煅烧后处理温度,研究了反应条件对乳液法自组装合成氧化锰纳米粒子结构、形貌和尺寸的影响.结果表明:当高锰酸钾与油酸物质的量比在1∶5～1∶1之间时,形成蜂窝状纳米粒子和空心纳米粒子;当分散相(油酸)与连续相(水)的体积比为4∶200时,形成良好的空心球纳米结构;反应体系温度升高不利于产物的洗涤;不同温度的煅烧后处理不仅影响氧化锰纳米粒子的形貌,而且影响其结晶度和晶型.     

CaCO3纳米微粒的层状液晶模板法制备及其生长过程中的形貌演变

在Triton X-100/n-C₁₀H₂₁OH/H₂O体系中，低角X射线衍射测试表明层状液晶的溶剂层厚度小于3 nm。利用层状液晶为模板制备了CaCO₃纳米微粒，并用透射电子显微镜(TEM)、X射线衍射(XRD)和选区电子衍射(SAED)进行了表征。TEM结果表明所得CaCO₃纳米粒子的形貌为球形，粒径在2～8 nm，分布较窄。XRD表明CaCO₃纳米微粒的物相为方解石型和球霰石型混合结构。在制备过程中，Ca(OH)₂的加入和CaCO₃纳米微粒的析出并未破坏层状液晶的对称性和长程有序性。此外，在Triton X-100/CH₃CH₂OH体系中，研究了CaCO₃纳米微粒的生长行为，发现小的纳米微粒先通过导向聚集生长成小的梭状物，然后小的梭状物继续生长，最后发生Ostwald陈化形成较为均一的两头尖的带状纳米结构，其宽度在50～200 nm，长度约为2 μm。     

PANI／Ce（OH）3-Pr2O3·3H2O／NanoG复合材料制备与表征

开发了反胶束模板-原位聚合纳米复合法制备聚苯胺（PANI）／Ce（OH）3-Pr2O3·3H2O／石墨纳米薄片（NanoG）纳米复合材料的方法。膨胀石墨在乙醇水溶液中经超声处理制得石墨纳米薄片,以苯胺的氯仿溶液为油相,稀土金属离子Pr^3＋、Ce^3＋水溶液为水相,依靠表面活性剂十六烷基三甲基溴化铵（CTAB）自组装形成的反胶束为模板。制备PANI／Ce（OH）3-Pr2O3·3H2O／NanoG复合材料。利用红外光谱（FTIR）、扫描电镜（SEM）、透射电镜（TEM）和X-射线衍射（XRD）对该复合材料进行了表征和分析,研究了其导电性能和热性能。结果表明,PANI／Ce（OH）3-Pr2O3·3H2O／NanoG复合材料各相分散均匀,稀土纳米粒子在体系中以棒状的形态分布。热重分析表明,该复合材料的热稳定性明显提高;导电性研究说明,石墨纳米薄片的特殊的结构（较大的径厚比）对其在聚合物基体中形成导电网络具有重要作用：PANI／Pr2O3-Ce（OH）3/NanoG纳米复合材料的渗滤阀值低于1.0wt％。     

反相胶束微乳液法制备氧化钇纳米微晶

纳米结晶;反相胶束微乳液法制备氧化钇纳米微晶     

水相法制备CdS纳米棒

水相法制备CdS纳米棒;cds纳米棒;水相溶液;晶体生长;乙二胺     

水热纳米浇筑HNTs模板法制备碳纳米棒

以埃洛石纳米管（HNTs）为模板和聚乙烯醇（PVA）为碳源,采用水热纳米浇筑法成功制备出碳纳米棒。方法涉及3步,即在HNTs中浇筑PVA,碳化和模板移除。采用一系列表征手段如XRD、FT-IR、SEM、TEM、Raman、XPS、SAED和N₂吸附-脱附等表征碳纳米棒的形成和结构。具有一维棒状结构的碳纳米棒具有高的比表面积（408 m²·g^-1）和典型的介孔特征。     

纳米碳纤维载铂作为质子交换膜燃料电池阳极催化剂

采用化学还原法合成了微结构不同的纳米碳纤维(板式、鱼骨式、管式)载铂催化剂(分别记为Pt/p-CNF、Pt/f-CNF、Pt/t-CNF). 通过高分辨透射电镜(HRTEM)和X射线衍射(XRD)等分析技术对催化剂的微观结构进行了表征, 并利用循环伏安(CV)法分析了催化剂的电化学比表面积(ESA). 在此基础上, 制备了膜电极(MEA), 通过单电池测试了催化剂的电催化性能. 结果表明: 铂纳米粒子在不同的纳米碳载体上表现出不同的粒径, 在板式、鱼骨式和管式纳米碳纤维上的铂纳米粒子平均粒径分别为2.4、2.7和2.8 nm. 板式纳米碳纤维载铂催化剂作单电池阳极时表现出良好的电催化性能, 其对应的最高功率密度可达0.569 W·cm^-2, 高于鱼骨式纳米碳纤维载铂催化剂和管式纳米碳纤维载铂催化剂对应的最高功率密度(分别为0.550和0.496 W·cm^-2). 同时, 也制备了碳黑(Pt/XC-72)载铂催化剂. 相比于Pt/XC-72, 纳米碳纤维载体上的铂纳米颗粒有较小的粒径、较好的分散和较高的催化活性, 说明纳米碳纤维是质子交换膜燃料电池(PEMFCs)催化剂的良好载体.     

水热纳米浇筑HNTs模板法制备碳纳米棒

以埃洛石纳米管（HNTs）为模板和聚乙烯醇（PVA）为碳源,采用水热纳米浇筑法成功制备出碳纳米棒。方法涉及3步,即在HNTs中浇筑PVA,碳化和模板移除。采用一系列表征手段如XRD、FT-IR、SEM、TEM、Raman、XPS、SAED和N₂吸附-脱附等表征碳纳米棒的形成和结构。具有一维棒状结构的碳纳米棒具有高的比表面积（409 m²·g^-1）和典型的介孔特征。     

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.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.