首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2152篇
  免费   545篇
  国内免费   190篇
化学   2358篇
晶体学   42篇
力学   37篇
综合类   17篇
数学   27篇
物理学   406篇
  2024年   7篇
  2023年   33篇
  2022年   68篇
  2021年   90篇
  2020年   130篇
  2019年   107篇
  2018年   90篇
  2017年   84篇
  2016年   191篇
  2015年   154篇
  2014年   131篇
  2013年   246篇
  2012年   173篇
  2011年   106篇
  2010年   122篇
  2009年   115篇
  2008年   106篇
  2007年   112篇
  2006年   103篇
  2005年   114篇
  2004年   74篇
  2003年   98篇
  2002年   86篇
  2001年   36篇
  2000年   23篇
  1999年   31篇
  1998年   17篇
  1997年   41篇
  1996年   28篇
  1995年   40篇
  1994年   10篇
  1993年   17篇
  1992年   25篇
  1991年   12篇
  1990年   12篇
  1989年   13篇
  1988年   8篇
  1987年   4篇
  1986年   2篇
  1985年   2篇
  1984年   9篇
  1983年   4篇
  1982年   2篇
  1981年   2篇
  1978年   2篇
  1975年   1篇
  1974年   2篇
  1973年   3篇
  1970年   1篇
排序方式: 共有2887条查询结果,搜索用时 46 毫秒
1.
The development of novel, tumor-selective and boron-rich compounds as potential agents for use in boron neutron capture therapy (BNCT) represents a very important field in cancer treatment by radiation therapy. Here, we report the design and synthesis of two promising compounds that combine meta-carborane, a water-soluble monosaccharide and a linking unit, namely glycine or ethylenediamine, for facile coupling with various tumor-selective biomolecules bearing a free amino or carboxylic acid group. In this work, coupling experiments with two selected biomolecules, a coumarin derivative and folic acid, were included. The task of every component in this approach was carefully chosen: the carborane moiety supplies ten boron atoms, which is a tenfold increase in boron content compared to the l-boronophenylalanine (l-BPA) presently used in BNCT; the sugar moiety compensates for the hydrophobic character of the carborane; the linking unit, depending on the chosen biomolecule, acts as the connection between the tumor-selective component and the boron-rich moiety; and the respective tumor-selective biomolecule provides the necessary selectivity. This approach makes it possible to develop a modular and feasible strategy for the synthesis of readily obtainable boron-rich agents with optimized properties for potential applications in BNCT.  相似文献   
2.
As a new type of quantum dots (QDs), hexagonal boron nitride quantum dots (BNQDs) exhibit promising potential in the applications of disease diagnosis, fluorescence imaging, biosensing, metal ion detection, and so on, because of their remarkable chemical stability, excellent biocompatibility, low cytotoxicity, and outstanding photoluminescence properties. However, the large-scale fabrication of homogeneous BNQDs still remains challenging. In this article, the properties and common fabrication methods of BNQDs are summarized based on the recent research progress. Then, the corresponding yields, morphologies, and fabrication mechanisms of these as-obtained BNQDs are discussed in detail. Moreover, the applications of these as-obtained BNQDs in different fields are also discussed. This article is expected to inspire new methods and improvements to achieve large-scale fabrication of homogeneous BNQDs, which will enable their practical applications in future.  相似文献   
3.
The B3NO2 six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B3NO2 ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.  相似文献   
4.
5.
In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).  相似文献   
6.
报道了N+离子轰击产生的氮化硼(BN)纳米结构,及在电子辐照时结构演化的高分辨透射电子显微镜的原位测定结果.应当强调的是,这种类富勒烯和发夹结构的演化,实际上是电子辐照诱发固态相变的发展,观察中发现的一些BN颗粒、卷曲物,可以被认为是类富勒烯等纳米结构形成的前体或早期阶段.提出了一种类富勒烯等结构的电子辐照动力学模型,并进行了讨论. 关键词: 氮化硼 电子辐照 透射电子显微镜 氮化硼纳米形成物  相似文献   
7.
A series of α,ω‐boryl(bromo)alkanes of the general formula R2B? (CH2)n? Br (n=3, 4, 5, 6) was obtained in high yield following a standard hydroboration protocol. Upon treatment with Mg turnings and formation of the respective Grignard species, all alkanes with n=4 to 6 underwent an unprecedented boron‐centered cyclisation reaction with formation of boratacyclopentanes, ‐hexanes, and ‐heptanes, respectively. All new compounds were isolated in high yields as colourless, crystalline materials and characterised in solution by multinuclear NMR spectroscopy. Four representative examples were chosen for X‐ray diffraction studies, thus providing the first structurally characterised ring systems of that size at a tetraalkyl borate centre.  相似文献   
8.
对不同的本底真空条件下,采用甚高频等离子体增强化学气相沉积技术沉积的氢化微晶硅(μc_Si∶H)薄膜中的氧污染问题进行了比较研究.对不同氧污染条件下制备的薄膜样品的x射线光电子能谱与傅里叶变换红外吸收光谱测量结果表明:μc_Si∶H薄膜中,氧以Si—O,O—O和O—H三种不同的键合模式存在,不同的键合模式源自不同的物理机理.μc_Si∶H薄膜的Raman光谱、电导率与激活能的测量结果进一步显示:沉积过程中氧污染程度的不同,对μc_Si∶H薄膜的结构特性与电学特性产生显著影响;而不同氧污染对μc_Si∶H薄膜电学特性的影响不同于氢化非晶硅(a_Si:H)薄膜. 关键词: 氢化微晶硅薄膜 甚高频等离子体增强化学气相沉积 氧污染  相似文献   
9.
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   
10.
 利用球磨法制备石墨-六角氮化硼微晶混合物,并在6.1 GPa、800~1 500 ℃条件下与水进行高压反应,以便研究用水作触媒合成B-C-N三元化合物的可能性。通过对反应产物的XRD、XPS谱分析发现:高压下随着温度的升高,反应产物中出现再结晶石墨,其晶化程度逐渐提高;但没有出现再结晶六角氮化硼,也未出现立方氮化硼。在球磨不充分条件下,石墨-六角氮化硼混合物的XRD谱没有完全弥散,它们与水高压反应时,能观察到石墨与立方氮化硼分别结晶的现象,但都没有形成B-C-N晶化结构。  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号