聚丙烯酰胺存在下微波高压合成银纳米粒子及其光谱特性

以聚丙烯酰胺为还原剂和稳定剂 ,采用微波高压液相合成法制备了黄色银纳米粒子。用吸收光谱和共振散射光谱研究了其制备条件的影响。在 4 2 1.6nm处产生最大吸收峰 ,在 4 70nm处产生一个最强共振散射峰。实验表明 :该法制备的银纳米粒子粒径均匀 ,平均粒径为 6 6nm ,其稳定性和分散性较好 ,合成方法简便、快捷。     

聚丙烯酰胺存在下微波高压合成银钠米粒子及其光谱特性

以聚丙烯酰胺为还原剂和稳定剂，采用微波高压液相合成法制备了黄色银钠米粒子。用吸收光谱和共振散射光谱研究了其制备条件的影响。在421.6nm处产生最大吸收峰，在470nm处产生一个最强共振散射峰。实验表明：该法制备的银钠米粒子粒径均匀，平均粒径为66nm，其稳定性和分散性较好，合成方法简便、快捷。     

共振散射光强度与金粒子粒径的关系

采用柠檬酸钠还原法制备了不同粒径的金粒子,并研究了金粒子的共振散射光谱.结果表明,金粒子在粒径10～95nm范围内呈红色,最大吸收波长在517.8～553.3nm范围内.随着金粒子粒径增大,吸收峰红移.粒径为10～95nm金粒子的最强共振散射峰位于580nm处,此波长处的共振散射光强度³√I与金粒子粒径d成正比.     

绿色银纳米粒子的共振散射光谱研究

以柠檬酸钠作光还原剂,采用紫外光-可见光二步光化学法制备了绿色银纳米离子,在399.4nm和691.5nm处有二个紫外-可见吸收峰;在340nm,470nm和520nm处有三个共振散射峰,从超分子和纳米粒子这一整体出发,探讨了共振散射光谱产生的原因及银超分子光反应机理。     

绿色银纳米粒子的共振散射光谱研究

以柠檬酸钠作光还原剂,采用紫外光-可见光二步光化学法制备了绿色银纳米离子,在399.4nm和691.5nm处有二个紫外-可见吸收峰;在340nm,470nm和520nm处有三个共振散射峰,从超分子和纳米粒子这一整体出发,探讨了共振散射光谱产生的原因及银超分子光反应机理。     

金纳米粒子的共振散射光谱

采用Frens 法制备了粒径为10～95 nm的金纳米粒子.它们均在580 nm处产生一个共振散射峰.从液相纳米粒子的波动观点出发,解释了金纳米粒子共振散射光谱的产生原因.用超分子界面能带理论解释了金纳米粒子的颜色与粒径的关系.根据最大吸收波长与粒径的关系,建立了一种测量金纳米粒子粒径的光度标尺.     

激光法连续制备纳米FeNi合金及其乙醇溶胶研究

采用脉冲激光轰击浸于流动乙醇中转动的FeNi合金固体靶连续制备得到纳米FeNi乙醇溶胶及其纳米合金. 能谱扫描测得纳米FeNi合金粒子Fe与Ni元素重量比约为66︰34; TEM观察纳米FeNi粒子初始粒径约为1~5 nm, 并随放置时间延长聚集长大; XRD显示纳米FeNi合金基本为非晶态; 荧光光谱发现纳米FeNi合金溶胶在311.00 nm处有一强的激发峰以及在273.00和347.00 nm处的二个弱激发峰, 以311.00 nm作为激发波长得到位于418.00 nm处的一强荧光光谱峰; UV-vis表明纳米FeNi合金溶胶在230.00 nm左右有一个含有一组可分辨的9个细峰的强吸收峰和一个位于275.00 nm处的弱激子吸收峰; FT-IR发现纳米FeNi/乙醇溶胶中乙醇缔合态羟基的伸缩振动吸收峰(υ_O-H)明显蓝移, 并且证实获得的纳米FeNi合金粒子表面在制备过程中为乙醇裂解产生的碳氢有机基团所修饰.     

CeO2@Au核壳结构纳米粒子的合成与性质研究

采用沉淀法制备了球形CeO2纳米粒子,将其作为核粒子溶液,然后向其中滴加四氯合金酸溶液,在CeO2胶体表面利用柠檬酸钠还原[AuCl4]-离子,得到了CeO2@Au核壳结构纳米粒子。TEM分析表明,CeO2纳米粒子分散效果好,粒径为5 nm;CeO2@Au核壳粒子为球形,无团聚,平均粒径为15 nm。XRD分析表明,CeO2@Au核壳粒子为晶型结构,属于立方晶系,CeO2空间群为O5H-FM3M,Au的空间群为Fm-3m。UV-vis分析发现,CeO2@Au核壳粒子在300和520 nm处呈现出两个比较强的吸收峰,分别对应于CeO2胶体溶液的吸收峰和金粒子的表面等离子共振吸收峰。EDS分析了核壳结构CeO2@Au纳米粒子中存在Ce,O和Au 3种元素。XPS分析表明,Ce3d3/2和Au4f电子结合能与标准结合能相比发生了变化,说明CeO2与Au之间存在着相互作用。     

维生素E绿色还原法制备银纳米粒子的研究

采用一种绿色还原法制备银纳米粒子,以维生素E为还原剂,淀粉为稳定剂,在液相中还原硫酸银,通过改变溶液的pH值和反应时间,得到不同粒径的黄色银纳米粒子,并分别采用透射电镜、红外光谱、紫外-可见吸收光谱、扫描电镜和电化学方法对银纳米粒子进行表征。结果表明:维生素E在溶液中被氧化生成苯醌,反应得到的银纳米粒子为球形,粒径为8~25 nm;在较强碱性条件下,得到的银纳米粒子尺寸较小,分布较均匀,其平均粒径约为10 nm;不同条件下生成的银溶胶分别在417、411、409、408 nm处出现紫外吸收峰,这些吸收峰均为银纳米粒子的表面共振吸收;生成的银纳米粒子具有很好的电化学性质,并对L-半胱氨酸的电化学反应显示了良好的催化活性。     

(AgBr)_核·(Ag)_壳纳米粒子的制备及其共振散射光谱研究

以 (AgBr) m 团簇作晶种 ,在柠檬酸钠存在条件下 ,(AgBr) m 团簇表面结合的Ag+被光化学还原而获得土红色的液相 (AgBr) 核·(Ag) 壳 纳米粒子 .研究了 (AgBr) 核·(Ag) 壳 纳米粒子的光谱特性 ,在 51 2nm处有最强共振散射峰 ,在41 0nm处产生一个吸收峰 .结果表明 ,(AgBr) 核·(Ag) 壳 纳米粒子的形成是导致51 2nm共振光散射的根本原因 .     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

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.