全文获取类型
收费全文 | 8477篇 |
免费 | 501篇 |
国内免费 | 258篇 |
专业分类
化学 | 5989篇 |
晶体学 | 57篇 |
力学 | 299篇 |
综合类 | 43篇 |
数学 | 1081篇 |
物理学 | 1767篇 |
出版年
2023年 | 103篇 |
2022年 | 155篇 |
2021年 | 184篇 |
2020年 | 176篇 |
2019年 | 231篇 |
2018年 | 166篇 |
2017年 | 131篇 |
2016年 | 273篇 |
2015年 | 231篇 |
2014年 | 282篇 |
2013年 | 476篇 |
2012年 | 618篇 |
2011年 | 644篇 |
2010年 | 372篇 |
2009年 | 353篇 |
2008年 | 532篇 |
2007年 | 528篇 |
2006年 | 485篇 |
2005年 | 470篇 |
2004年 | 431篇 |
2003年 | 372篇 |
2002年 | 313篇 |
2001年 | 177篇 |
2000年 | 128篇 |
1999年 | 118篇 |
1998年 | 107篇 |
1997年 | 100篇 |
1996年 | 107篇 |
1995年 | 85篇 |
1994年 | 61篇 |
1993年 | 50篇 |
1992年 | 48篇 |
1991年 | 49篇 |
1990年 | 68篇 |
1989年 | 44篇 |
1988年 | 28篇 |
1987年 | 23篇 |
1986年 | 40篇 |
1985年 | 34篇 |
1984年 | 42篇 |
1983年 | 31篇 |
1982年 | 39篇 |
1981年 | 27篇 |
1980年 | 38篇 |
1979年 | 28篇 |
1978年 | 33篇 |
1977年 | 39篇 |
1976年 | 28篇 |
1975年 | 29篇 |
1973年 | 19篇 |
排序方式: 共有9236条查询结果,搜索用时 15 毫秒
121.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
122.
John Fielden Patrick T. Gunning De-Liang Long Margaret Nutley Arkady Ellern Paul Kgerler Leroy Cronin 《Polyhedron》2006,25(18):3474-3480
The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H2O)(NO3)](NO3) (1), and [Zn(DDOP)(H2O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode. 相似文献
123.
Patrick DL Flanagan JF Kohl P Lynden-Bell RM 《Journal of the American Chemical Society》2003,125(22):6762-6773
Chemical force microscopy and related force measurement techniques have emerged as powerful tools for studying fundamental interactions central to understanding adhesion and tribology at the molecular scale. However, detailed interpretation of these interactions requires knowledge of chemical and physical processes occurring in the region of the tip-sample junction that experiments cannot provide, such as atomic-scale motions and distribution of forces. In an effort to address some of these open issues, atomistic molecular dynamics simulations were performed modeling a chemical force microscope stylus covered with a planar C12 alkylthiolate self-assembled monolayer (SAM) interacting with a solid wall. A complete loading-unloading sequence was simulated under conditions of near-constant equilibrium, approximating the case of infinitely slow tip motion. In the absence of the solid wall, the stylus film existed in a fluid state with structural and dynamic properties similar to those of the analogous planar SAM at an elevated temperature. When the wall was brought into contact with the stylus and pressed against it, a series of reversible changes occurred culminating with solidification of the SAM film at the largest compressive force. During loading, the chemical composition of the contact changed, as much of the film's interior was exposed to the wall. At all tip heights, the distribution of forces within the contact zone was uneven and subject to large local fluctuations. Analysis using the Johnson-Kendall-Roberts, Derjaguin-Muller-Toporov, and Hertz contacts mechanics models revealed significant deviations from the simulation results, with the JKR model providing best overall agreement. Some of the discrepancies found would be overlooked in an actual experiment, where, unlike the simulations, contact area is not separately known, possibly producing a misleading or incorrect interpretation of experimental results. These shortcomings may be improved upon by using a model that correctly accounts for the finite thickness of the compliant components and nonlinear elastic effects. 相似文献
124.
É. Fenyvesi A. Ujházy J. Szejtli S. Potter T. G. Gan 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):185-189
Various disinfecting drugs (ethacridine lactate, methylene blue, gentian violet, brilliant green, fuchsin acid, cetylpyridinium chloride) were incorporated into CD bead polymers substituted with carboxymetbyl groups and a retarded release rate was measured. These polymers were successfully used as sustained release wound powders as well as in chewing gum formulations. 相似文献
125.
A novel pyridinium salt photoelectrocyclization-nucleophilic bicyclic aziridine ring opening reaction sequence has been investigated in order to determine its preparative potential. N-Alkylpyridinium perchlorates were found to undergo photoinduced electrocyclization upon irradiation in nucleophilic solvents, such as H(2)O and MeOH, to efficiently produce 6-alkyl-6-azabicyclo[3.1.0]hex-2-en-4-yl alcohols and ethers. The bicyclic aziridine photoproducts react with a number of different nucleophiles (e.g., H(2)O, MeOH, AcOH, AcSH) under acid-catalyzed conditions to produce 5-(nucleophile-substituted)-4-(alkylamino)cyclopenten-3-yl alcohols and ethers. The aziridine ring opening processes are both regioselective and stereoselective, yielding trans,trans-trisubstituted cyclopentenes exclusively, apparently as a consequence of the operation of an SN(2) mechanism. The effects of C-alkyl substitution on the regiochemistry of the pyridinium cation photocyclization reaction were briefly probed, and a method was developed to produce trans,cis-trisubstituted cyclopentenes by use of this tandem preparative sequence. 相似文献
126.
The m6A‐RNA modification is a dynamic and reversible process, which has emerged as a new RNA code for the regulation of gene expression. The functional network of methyltransferases (writers), demethylases (erasers), and binding proteins (readers) modulate the level of m6A modification. Dysfunction of RNA methylation has been associated with various fundamental biological processes and human diseases. Herein, we briefly introduce an understanding‐enabled manipulation on m6A‐RNA modification with an emphasis on the use of small‐molecule intervention. 相似文献
127.
The three-photon absorption effect (3PA) of two novel symmetrical charge transfer fluorene-based molecules (abbreviated as BASF and BMOSF) has been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 84 × 10−78 and 114 × 10−78 cm6 s2, respectively. The geometries and electronic excitations of these two molecules are systematically studied by PM3 and ZINDO/S methods. The relationships between 3PA cross-sections and intramolecular charge transfer are discussed micromechanically. The experimental and theoretical results have shown that the larger intramolecular charge transfer, which was characterized by the charge density difference between the ground state (S0) and the first excited state (S1), the greater enhancement of the 3PA cross-sections. 相似文献
128.
Mousumi Sannigrahi Patrick Pinto T.M. Chan Neng-Yang Shih F. George Njoroge 《Tetrahedron letters》2006,47(28):4877-4880
An efficient and practical synthesis of sterically hindered N-substituted lactams has been developed starting from simple starting materials. The stereochemistry of the synthetically useful N,N acetal intermediate has been established. 相似文献
129.
Volumetric heat capacities of the six binary mixtures formed from cyclopentane, cyclohexane, cycloheptane and cyclooctane were determined at 298.15 K in a Picker flow microcalorimeter. Excess heat capacities obtained from the results are compred with the temperature variation of excess enthalpies from the literature. 相似文献
130.
In this Communication, we outline a new one-pot, multicomponent coupling reaction that allows easy access to (Z)-trisubstituted allylic alcohols. Our strategy is based on E to Z isomerization of the 1-bromo-1-dialkylvinylborane upon reaction with dialkylzinc reagents, and subsequent transmetalation to give (Z)-trisubstituted vinylzinc species. In situ trapping of the reactive vinylzinc intermediates with aldehydes furnished a series of (Z)-trisubstituted allylic alcohols. This method represents a viable alternative to the Still-Gennari modification of the HWE olefination reaction, and it has the advantage that it allows coupling of larger fragments. 相似文献