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.     

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.     

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。     

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 .     

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.     

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.     

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%).     

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.     

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.     

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.