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   4212篇
  免费   223篇
  国内免费   20篇
化学   2880篇
晶体学   45篇
力学   85篇
数学   635篇
物理学   810篇
  2023年   34篇
  2022年   41篇
  2021年   65篇
  2020年   82篇
  2019年   84篇
  2018年   78篇
  2017年   81篇
  2016年   195篇
  2015年   157篇
  2014年   139篇
  2013年   247篇
  2012年   284篇
  2011年   294篇
  2010年   182篇
  2009年   137篇
  2008年   255篇
  2007年   222篇
  2006年   180篇
  2005年   184篇
  2004年   174篇
  2003年   151篇
  2002年   137篇
  2001年   47篇
  2000年   49篇
  1999年   45篇
  1998年   45篇
  1997年   40篇
  1996年   53篇
  1995年   28篇
  1994年   36篇
  1993年   44篇
  1992年   36篇
  1991年   33篇
  1990年   30篇
  1989年   34篇
  1988年   36篇
  1987年   30篇
  1986年   26篇
  1985年   45篇
  1984年   38篇
  1983年   18篇
  1982年   24篇
  1981年   19篇
  1980年   23篇
  1979年   26篇
  1978年   27篇
  1977年   27篇
  1975年   22篇
  1974年   19篇
  1973年   21篇
排序方式: 共有4455条查询结果,搜索用时 15 毫秒
71.
The chiral recognition capabilities of three macrocyclic glycopeptide chiral selectors, namely teicoplanin (Chirobiotic T), its aglycone (Chirobiotic TAG) and ristocetin (Chirobiotic R), were evaluated with supercritical and subcritical fluid mobile phases. A set of 111 chiral compounds including heterocycles, analgesics (nonsteroidal antiinflamatory compounds), beta-blockers, sulfoxides, N-protected amino acids and native amino acids was separated on the three chiral stationary phases (CSPs). All separations were done with an outlet pressure regulated at 100 bar, 31 degrees C and at 4 ml/min. Various amounts of methanol ranging from 7 to 67% (v/v) were added to the carbon dioxide along with small amounts (0.1 to 0.5%, v/v) of triethylamine and/or trifluoroacetic acid. The Chirobiotic TAG CSP was the most effective closely followed by the Chirobiotic T column. Both columns were able to separate, partially or fully, 92% of the enantiomers of the compound set. The ristocetin chiral selector could partially or baseline resolve only 60% of the enantiomers tested. All separations were done in less than 15 min and 70% were done in less than 4 min. The speed of the separations is the main advantage of the use of SFC compared to normal-phase HPLC. In addition, SFC is advantageous for preparative separations with easy solute recovery and solvent disposal.  相似文献   
72.
Cofino et al. have put forward a method for the analysis of data from interlaboratory studies. The method uses ideas and notation from quantum chemistry, and is quite sophisticated. A critical examination shows that it has some relationship with both kernel density estimation and robust estimation methods. The quantitative results it provides are not founded on any statistical probability model, and it is not at all clear how the variance in particular is to be interpreted. There is no clear argument for adopting Cofino statistics in preference to simple problem-free methods that are at least as effective in estimating a concensus value.This report was prepared for the Statistical Subcommittee by Professor T. Fearn, with the assistance of Mr T. Robinson, and approved by the AMC on 25/11/03. The Statistical Subcommittee comprised: Dr. S.L.R. Ellison, Professor T. Fearn, Mr M. Gardner, Dr. F. Hollywood, Professor R.J. Howarth, Dr. P. Lowthian, Professor J.N. Miller, Dr. E.J. Newman, Professor B.D. Ripley, Professor M. Thompson (Chair), Dr. R. Wood, Dr. A. Williams and Mr J.J. Wilson (Secretary).  相似文献   
73.
Wu TY  Schultz PG  Ding S 《Organic letters》2003,5(20):3587-3590
[reaction: see text] A microwave-assisted reaction was developed to facilitate the construction of 4,5-disubstituted pyrazolopyrimidines. This one-pot two-step process involves a sequential S(N)Ar displacement of the C4 chloro substituent with various anilines and amines, followed by a Suzuki coupling reaction with different boronic acids. Using microwave irradiation leads to high product conversion, low side product formation, and shorter reactions.  相似文献   
74.
Principles of droplet electrohydrodynamics for lab-on-a-chip   总被引:7,自引:0,他引:7  
Zeng J  Korsmeyer T 《Lab on a chip》2004,4(4):265-277
Electrically controlled droplet-based labs-on-a-chip operate under the principles of electro-capillarity and dielectrophoresis. The microfluidic mechanics of manipulating electrified droplets are complex and not entirely understood. In this article, we analyse these operating principles, especially electrowetting on dielectric (a form of electro-capillarity) and dielectrophoresis, under a unified framework of droplet electrohydrodynamics. We differentiate them by their electric origins and their energy transduction mechanisms. Our study shows that both electrowetting on dielectric and dielectrophoresis are effective for droplet generation and manipulation. In addition, our study demonstrates: (1) the presence of a wetting contribution to dielectrophoresis; and (2) contact angle reduction is merely an observable consequence of, not a condition for, the occurrence of electrowetting on dielectric. Simulations are used extensively in this article to illustrate device operation, to expose underlying physics, and to validate our conclusions. Simulations of electrically driven droplet generation, droplet translocation, droplet fusion, and droplet fission are presented.  相似文献   
75.
A systematic investigation of the influence of the perimeter shape of open and particle packed fused silica capillaries on chromatographic properties such as resistance to flow and dispersion of solutes propelled through these channels has been conducted. Verifications of these uncommon experiments with existing theoretical treatments are presented and the insights transferred to a novel polymer chip design with integrated facilities for complex separations. A comparison of the chromatographic performance of a real life proteomics sample on this chip with a capillary column of "similar" dimensions is presented.  相似文献   
76.
The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO4)2·H2O,γ-Ti(PO4)(H2PO4)·2H2O, and its anhydrous formβ-Ti(PO4)(H2PO4). The structure ofβ-Ti(PO4)(H2PO4) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP21/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:Rp=2.9% andRwp=3.8%. The structure ofβ-Ti(PO4)(H2PO4) is built from TiO6octahedra linked together by tertiary phosphate (PO4) and dihydrogen phosphate ((OH)2PO2) tetrahedra. The layers are held together by hydrogen bonds.  相似文献   
77.
Glyoxaldiimines (I) RN=CHCH=NR show in the NMR a downfield shift of glyoxalic protons (Hgly) when complexed to
(II: M = Mo, W), but increasing high field shifts when going to
(III) and
complexes (IV). In the tungsten complexes II HglyW coupling satellites are resolved (J(WH) ≈4–6 Hz); in the phosphine compounds III, IV long range PHgly coupling is clearly visible. Mechanisms of spinspin interaction are briefly discussed in connection with the EPR results on monoanionic radicals of II–IV.  相似文献   
78.
79.
Summary We describe an approach to protein structure comparison designed to detect distantly related proteins of similar fold, where the procedure must be sufficiently flexible to take into account the elasticity of protein folds without losing specificity. Protein structures are represented as a series of secondary structure elements, where for each element a local environment describes its relations with the elements that surround it. Secondary structures are then aligned by comparing their features and local environments. The procedure is illustrated with searches of a database of 468 protein structures in order to identify proteins of similar topology to porcine pepsin, porphobilinogen deaminase and serum amyloid P-component. In all cases the searches correctly identify protein structures of similar fold as the search proteins. Multiple cross-comparisons of protein structures allow the clustering of proteins of similar fold. This is exemplified with a clustering of /- and -class protein structures. We discuss applications of the comparison and clustering of three-dimensional protein structures to comparative modelling and structure-based protein design.  相似文献   
80.
Improved Surrogate Data for Nonlinearity Tests   总被引:2,自引:0,他引:2  
  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