纳米材料研究进展Ⅰ：纳米材料结构与化学性质

报导了上年来有关钠米化学领域研究的某些进展。阐述了纳米材料的特征结构与独特的化学性质。     

抗肿瘤纳米材料

<正>蓬勃发展的纳米材料为肿瘤的安全高效治疗提供了有潜力的平台,其主要应用于肿瘤精确诊断、药物靶向递送、微环境调控和自身免疫系统激活等方面^[1-2]。本文简述了该领域发表于《应用化学》上的最新研究成果,并展望了抗肿瘤纳米材料在临床应用中的机遇与挑战。     

稀土纳米材料的制备与组装

稀土元素具有特殊的电子构型，使其在许多领域得到十分广泛的应用。稀土纳米化将有助于发现新性质、开拓新材料，因此，稀土纳米材料已经成为研究的热点。综述了各种形态稀土纳米材料的制备和性质、稀土纳米材料的复合与组装等方面的进展。     

跨世纪的新材料——纳米材料

纳米材料是２１世纪最有前途的新型材料之一，世界各国对这种新材料给予极大的关注，本文介绍了纳米材料的基本概念，基本结构特性，以及它的制备，表征和应用。     

纳米材料及其光学特性

纳米材料是纳米科学技术的重要发展方向之一。本文综述了纳米材料线性和非线性光学等特性的研究进展，以期使纳米材料的光学特性得到更加深入细致的研究。     

纳米材料的结构分析

介绍宏观与微观的纳米粒子具有特殊的结构与性能,采用现代分析测试技术确定纳米材料的结构,并探索其原子或分子组成的规律是目前纳米科学的最微处理的研究内容之一。评述了纳米材料结构分析方法及理论研究的新成果。     

无机层状纳米材料与聚苯胺的复合研究

聚苯胺被认为是最有希望在实际中得到广泛应用的导电聚合物，通过与无机层状纳米材料的复合改性，其复合物在二次电池电解质、光电转换、热电、磁电、电致流变等新材料领域显示出诱人前景。本文对无机层状材料与聚苯胺的复合方法、复合物性质及其应用前景进行了评述。     

纳米材料的自组装研究进展

本文主要评述了近年来纳米材料自组装的研究进展，即对以纳米材料(包括零维的纳米粒子和一维的纳米管/线)为单元而开展的自组装方面的工作进行了介绍。将纳米材料自组装为各种尺度的有序结构会产生更优异的整体的协同性质，这对于以纳米材料为基础而构筑的微纳米器件有着重要的意义。由于目前纳米材料的研究主要集中在零维和一维体系，因此，本文分别就此两种体系的自组装行为进行了评述。具体内容包括：单分子层薄膜修饰的无机纳米粒子的自组装、大分子修饰的无机纳米粒子的自组装、未被修饰的无机纳米粒子的自组装；表面张力及毛细管力诱导的一维纳米材料的自组装、模板诱导的一维纳米材料的自组装、静电力诱导的一维纳米材料的自组装。     

纳米材料的毒理学研究进展

在过去的几十年时间里,纳米材料已经被广泛运用到美容、食品、工程、医疗等领域.伴随着纳米材料的普及,这些材料对人体、环境展现出的毒理特征也逐渐引起了人们的关注.本文就纳米材料进入人体的传播途径(皮肤传递、呼吸和消化系统)、纳米材料对机体的毒性、纳米材料的理化性质(尺寸、形状、表面修饰、表面电荷)对纳米材料毒理性的影响以及现有的纳米毒理学研究方法进行概括与总结.该论述可为国内纳米材料研究工作者提供参考与借鉴.     

ISO发布纳米材料分类新标准

不久前，国际标准化组织（ISO）发布《纳米材料分类的新标准——ISO／TR11360：2010》。该标准为纳米材料的分类提供了更综合、更国际化的方法。     

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.     

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.     

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.     

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.