溶胶-凝胶法制备镶嵌在SiO_2玻璃中的InAs纳米晶

以As2 O3,InCl3·4H2 O和正硅酸乙酯为原料 ,通过水解、缩聚制备了xIn2 O3-xAs2 O3- 10 0SiO2 (x =0 .5～ 7.5 )凝胶 .在氧气中加热到 45 0℃对凝胶热处理使其转化成凝胶玻璃 ,再在 2 0 0～ 5 0 0℃与氢气反应 ,结果在SiO2 凝胶玻璃中形成了立方相InAs.利用XRD测试了InAs纳米颗粒的大小 ,发现随着反应温度的升高及掺杂量的增加 ,InAs纳米颗粒粒径从 6增大到 2 9nm .电子衍射表明凝胶玻璃中的InAs纳米颗粒为多晶结构     

湿化学法制备的KTiOPO4@SiO2玻璃陶瓷纳米结构和透明性

用湿化学法合成了25KTiOPO4-75SiO2透明纳米玻璃陶瓷。采用X射线衍射、场发射扫描电子显微镜和二次谐波发生对玻璃陶瓷物相及纳米结构进行了分析。透明凝胶块经过热处理后,从SiO2基玻璃中析出了粒径为~30 nm的KTiOPO4纳米晶体,形成了透明KTiOPO4@SiO2纳米玻璃陶瓷;凝胶粒子的烧结致密化消除了大量不规则介孔,但形成了少量30 nm的球状孔;这种相对致密的玻璃陶瓷在可见光波段的光学透射率为64%左右。根据纳米结构数据,利用瑞利散射模型分析了纳米结构对玻璃陶瓷透明性的影响,结果表明,KTiOPO4晶体与SiO2玻璃相折射率之差是降低致密纳米玻璃陶瓷透明性的主要因素。     

掺锗SiO2 玻璃的发光现象

掺锗SiO2 玻璃的发光现象;Ge/SiO2玻璃;Ge纳米晶粒;溶胶-凝胶;光致发光     

溶胶－凝胶法制备镶嵌在SiO2玻璃中的InAs纳米晶

以As2O3,InCl3·4H2O和正硅酸乙酯为原料,通过水解、缩聚制备了xIn2O3-xAs2O3-100SiO2(x=0.5～7.5)凝胶,在氧气中加热到450℃对凝胶热处理使其转化成凝胶玻璃,再在200～500℃与氢气反应,结果在SiO2凝胶玻璃中形成了立方相InAs,利用XRD测试了InAs纳米颗粒的大小、发现随着反应温度的升高及掺杂量的增加,InAs纳米颗粒粒径从6增大到29nm,电子衍射表明凝胶玻璃中的InAs纳米颗粒为多晶结构。     

PbF_2·SiO_2基玻璃陶瓷的溶胶-凝胶法制备及结构转变研究

采用溶胶-凝胶法制备了 PbF2?SiO2纳米晶玻璃陶瓷块体;利用 TG-DSC 和 IR 技术分析了干凝胶在热处理过程中有机基团的分解及内部原子键合方式的演变;结合 XRD 和 TEM 研究了凝胶玻璃中 PbF2纳米晶粒的长大过程,并分析了 Er3+掺杂的影响。结果表明,采用此方法制备的 PbF2?SiO2纳米晶玻璃陶瓷具有较好的成形性,晶化温度在 320℃左右;经 480℃热处理,镶嵌在玻璃基体中的 PbF2晶粒尺度约为 10～25nm,材料透明性良好。在 PbF2?SiO2系统中掺入少量的 Er3+,将提高 PbF2的晶化温度,降低玻璃陶瓷的显微硬度;掺杂可能对 PbF2晶粒表面原子的活性起抑制作用,阻碍晶粒的表面迁移,使晶粒的生长速度明显降低。     

PbF2·SiO2基玻璃陶瓷的溶胶-凝胶制备及结构转变研究

采用溶胶-凝胶法制备了PbF2·SiO2纳米晶玻璃陶瓷块体;利用TG-DSC和IR技术分析了干凝胶在热处理过程中有机基团的分解及内部原子键合方式的演变;结合XRD和TEM研究了凝胶玻璃中PbF2纳米晶粒的长大过程,并分析了Er3+掺杂的影响.结果表明,采用此方法制备的PbF2.SiO2纳米晶粒玻璃陶瓷具有较好的成形性,晶化温度在320℃左右;经480℃热处理,镶嵌在玻璃基体中的PbF2晶粒尺度约为10-25nm,材料透明性良好.在PbF2·SiO2系统中掺入少量的Er3+,将提高PbF2的晶化温度,降低玻璃陶瓷的显微硬度;掺杂可能对PbF2晶粒表面原子的活性起抑制作用,阻碍晶粒的表面迁移,使晶粒的生长速度明显降低.     

湿化学法制备的KTiOPO4@SiO2玻璃陶瓷纳米结构和透明性

用湿化学法合成了25KTiOPO₄-75SiO₂透明纳米玻璃陶瓷。采用X射线衍射、场发射扫描电子显微镜和二次谐波发生对玻璃陶瓷物相及纳米结构进行了分析。透明凝胶块经过热处理后,从SiO₂基玻璃中析出了粒径为~30 nm的KTiOPO₄纳米晶体,形成了透明KTiOPO₄@SiO₂纳米玻璃陶瓷;凝胶粒子的烧结致密化消除了大量不规则介孔,但形成了少量30 nm的球状孔;这种相对致密的玻璃陶瓷在可见光波段的光学透射率为64%左右。根据纳米结构数据,利用瑞利散射模型分析了纳米结构对玻璃陶瓷透明性的影响,结果表明,KTiOPO₄晶体与SiO₂玻璃相折射率之差是降低致密纳米玻璃陶瓷透明性的主要因素。     

钕掺杂磷酸盐微晶玻璃的制备及表征

利用熔融和晶化技术制备掺钕磷酸盐玻璃陶瓷。 采用差热分析、X射线衍射、扫描电子显微镜、紫外 可见 近红外分光光度计及荧光光谱仪对材料进行表征和分析。 结果表明,在490～540 ℃核化1～2 h,在550 ℃晶化1～3 h,可制得主晶相为Al2SiO5的透明玻璃陶瓷。 其透过率可达69%,晶粒平均尺寸为90 nm,并随热处理时间的增加逐渐增大,但透过率降低。 由于Nd3+在热处理后进入到Al2SiO5晶相中,使荧光谱线在1 056 nm处峰值比原始玻璃强度大。     

燃烧法制备纳米晶氧化镍

纳米氧化镍可用作热敏元件、功能陶瓷、催化剂、玻璃、电极材料、涂料、气敏原件、电子元件等。目前文献制备的纳米氧化镍的方法有微波热分解法、化学沉淀法、溶胶-凝胶法、高分子网络法、离子交换树脂法、电化学法、共沸蒸馏法等。本文在500℃的马福炉中合成了面心立方晶系的纳米晶氧化镍,颗粒平均直径约为10nm,该法具有操作简便和省时等优点。     

钕掺杂磷酸盐玻璃陶瓷的制备及表征

利用熔融和晶化技术制备掺钕磷酸盐玻璃陶瓷.采用差热分析、X射线衍射、扫描电子显微镜、紫外-可见-近红外分光光度计及荧光光谱仪对材料进行表征和分析.结果表明,在490～540 ℃核化1～2 h,在550 ℃晶化1～3 h,可制得主晶相为Al2SiO5的透明玻璃陶瓷.其透过率可达69%,晶粒平均尺寸为90 nm,并随热处理时间的增加逐渐增大,但透过率降低.由于Nd3+在热处理后进入到Al2SiO5晶相中,使荧光谱线在1 056 nm处峰值比原始玻璃强度大.     

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.