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   2980篇
  免费   757篇
  国内免费   436篇
化学   3051篇
晶体学   105篇
力学   54篇
综合类   19篇
数学   32篇
物理学   912篇
  2024年   14篇
  2023年   52篇
  2022年   137篇
  2021年   116篇
  2020年   214篇
  2019年   161篇
  2018年   140篇
  2017年   143篇
  2016年   268篇
  2015年   213篇
  2014年   178篇
  2013年   300篇
  2012年   228篇
  2011年   177篇
  2010年   193篇
  2009年   178篇
  2008年   163篇
  2007年   185篇
  2006年   163篇
  2005年   139篇
  2004年   102篇
  2003年   134篇
  2002年   99篇
  2001年   61篇
  2000年   40篇
  1999年   48篇
  1998年   28篇
  1997年   58篇
  1996年   36篇
  1995年   45篇
  1994年   18篇
  1993年   26篇
  1992年   21篇
  1991年   13篇
  1990年   17篇
  1989年   12篇
  1988年   10篇
  1987年   5篇
  1986年   5篇
  1985年   5篇
  1984年   6篇
  1983年   4篇
  1982年   4篇
  1981年   2篇
  1979年   3篇
  1975年   1篇
  1974年   2篇
  1973年   3篇
  1970年   1篇
  1968年   1篇
排序方式: 共有4173条查询结果,搜索用时 0 毫秒
1.
Herein, we propose the construction of a sandwich-structured host filled with continuous 2D catalysis–conduction interfaces. This MoN-C-MoN trilayer architecture causes the strong conformal adsorption of S/Li2Sx and its high-efficiency conversion on the two-sided nitride polar surfaces, which are supplied with high-flux electron transfer from the buried carbon interlayer. The 3D self-assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN-C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job-synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li2Sx, and avoids thick and devitalized accumulation (electrode passivation) even after high-rate and long-term cycling.  相似文献   
2.
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   
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.
Multi-quantum well heterostructures (MQWHs) of the novel Ga(NAsP)/GaP material system have been grown, pseudomorphically strained to GaP-substrate. The crystalline perfection is verified by transmission electron microscopy (TEM). For As-concentrations in excess of about 70%, a direct band structure and adequate luminescence efficiency for laser device application is observed. Temperature-dependent photoluminescence (PL) investigations show the influence of carrier localisation and non-radiative recombination processes typical for dilute nitride materials. With rising N content in the active material, the emission wavelength shifts towards longer wavelength, leading to Ga(NAs)/GaP MQW structures with photon energies below the indirect band gap of silicon (Si). At the same time the luminescence intensity drops due to an increase in non-radiative carrier traps and/or structural degradation.  相似文献   
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.
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   
7.
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   
8.
Synthesis and Structure of K3N Two phases in the binary system K/N have been obtained via co‐deposition of potassium and nitrogen onto polished sapphire at 77 K and subsequent heating to room temperature. The powder diffraction pattern of one of these phases can be satisfactorily interpreted by assuming the composition K3N, and the anti‐TiI3 structure‐type, which is also adopted by Cs3O. The resulting hexagonal lattice constants are: a = 779.8(2), c = 759.2(9) pm, Z = 2, P63/mcm. Comparison with possible structures of K3N generated by computational methods and refined at Hartree‐Fock‐ and DFT level, reveals that the energetically most favoured structure has not formed (presumable Li3P‐type), but instead one of those with very low density. In this respect, the findings for K3N are analogous to the results on Na3N. The thermal evolution of the deposited starting mixture has been investigated. Hexagonal K3N transforms to another K/N phase at 233 K. Its XRD can be fully indexed resulting in an orthorhombic cell a = 1163, b = 596, c = 718 pm. Decomposition leaving elemental potassium as the only residue occurs at 263 K.  相似文献   
9.
氮化硼固相转变的船形模型   总被引:1,自引:1,他引:0       下载免费PDF全文
 船形转变模型是有rBN结构向wBN结构的固相转变模型。在静高压下,相比于以椅形方式,rBN更容易以船形方式转变。  相似文献   
10.
The performance of high power transistor devices is intimately connected to the substrate thermal conductivity. In this study, the relationship between thermal conductivity and dislocation density is examined using the 3 omega technique and free standing HVPE GaN substrates. Dislocation density is measured using imaging cathodoluminescence. In a low dislocation density regime below 105 cm−2, the thermal conductivity appears to plateau out near 230 W/K m and can be altered by the presence of isotopic defects and point defects. For high dislocation densities the thermal conductivity is severely degraded due to phonon scattering from dislocations. These results are applied to the design of homoepitaxially and heteroepitaxially grown HEMT devices and the efficiency of heat extraction and the influence of lateral heat spreading on device performance are compared.  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