全文获取类型
收费全文 | 29356篇 |
免费 | 1326篇 |
国内免费 | 279篇 |
专业分类
化学 | 19945篇 |
晶体学 | 275篇 |
力学 | 1023篇 |
综合类 | 4篇 |
数学 | 2510篇 |
物理学 | 7204篇 |
出版年
2023年 | 175篇 |
2022年 | 342篇 |
2021年 | 571篇 |
2020年 | 506篇 |
2019年 | 535篇 |
2018年 | 405篇 |
2017年 | 368篇 |
2016年 | 828篇 |
2015年 | 745篇 |
2014年 | 908篇 |
2013年 | 1642篇 |
2012年 | 2182篇 |
2011年 | 2372篇 |
2010年 | 1445篇 |
2009年 | 1269篇 |
2008年 | 1924篇 |
2007年 | 1793篇 |
2006年 | 1670篇 |
2005年 | 1570篇 |
2004年 | 1362篇 |
2003年 | 1045篇 |
2002年 | 1040篇 |
2001年 | 714篇 |
2000年 | 611篇 |
1999年 | 380篇 |
1998年 | 279篇 |
1997年 | 318篇 |
1996年 | 358篇 |
1995年 | 281篇 |
1994年 | 295篇 |
1993年 | 289篇 |
1992年 | 276篇 |
1991年 | 226篇 |
1990年 | 169篇 |
1989年 | 145篇 |
1988年 | 146篇 |
1987年 | 125篇 |
1986年 | 95篇 |
1985年 | 173篇 |
1984年 | 114篇 |
1983年 | 107篇 |
1982年 | 123篇 |
1981年 | 90篇 |
1980年 | 86篇 |
1978年 | 84篇 |
1977年 | 87篇 |
1976年 | 97篇 |
1975年 | 102篇 |
1974年 | 80篇 |
1973年 | 103篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K. 相似文献
992.
Miklos Kertesz Yong S. Lee James J. P. Stewart 《International journal of quantum chemistry》1989,35(2):305-313
It is shown that infinite long polyacene chains may have three energetically close but structurally distinct isomers (a symmetrical, sym, form and two lower symmetry forms: one with double bonds in a trans and another isomer with double bonds in a cis pattern). The energetics is based on solid state MNDO theory. We discuss that the symmetrical form has a substantial energy gap Eg in the Hartree–Fock approach owing to exact exchange terms, which are nonlocal. Broken symmetry Hartree–Fock (HF ) solutions for polyacene are also described. An angularly distorted structure suggested earlier on Jahn–Teller grounds is found to be energetically not favorable. 相似文献
993.
Asao N Takahashi K Lee S Kasahara T Yamamoto Y 《Journal of the American Chemical Society》2002,124(43):12650-12651
The reaction of o-alkynylbenzaldehydes 1 and alkynes 2 in the presence of a catalytic amount of AuCl3 in (CH2Cl)2 at 80 degrees C gave naphthyl ketone products in high yields. The AuCl3-catalyzed formal [4 + 2] benzannulation proceeds most probably through the coordination of the triple bond of 1 to AuCl3, the formation of benzo[c]pyrylium auric ate complex via the nucleophilic addition of the carbonyl oxygen atom, the Diels-Alder addition of alkynes 2 to the auric ate complex, and subsequent bond rearrangement. Similarly, the AuCl3-catalyzed reactions of o-alkynylacetophenone and o-alkynylbenzophenone with phenylacetylene afforded the corresponding naphthyl ketone products in good yields. 相似文献
994.
A chemically modified platinum electrode with coated poly[tetra(4-aminophenyl)porphyrin] has been used as a potentiometric pH sensor. It gives a linear response over the pH range 1.5-13.7 with a slope of 55 mV/pH (at 20 degrees ). The sensor has fair resistance to erosion of hydrofluoric acid and to interference of a coexisting redox couple. The sensor can be used for pH determination and end-point indication for potentiometric titration of hydrofluoric acid with sodium hydroxide. The a.c. impedance of the polymer membrane has also been studied. 相似文献
995.
996.
997.
J. W. Lee S. J. Pearton C. J. Santana E. S. Lambers C. R. Abernathy W. S. Hobson F. Ren 《Plasma Chemistry and Plasma Processing》1996,16(3):365-378
Electron cyclotron resonance (ECR) plasma etching with additional rf-biasing produces etch rates 2,500 A/min for InGaP and AlInP in CH4/H2/Ar. These rates are an order of magnitude or much higher than for reactive ion etching conditions (RIE) carried out in the same reactor. N2 addition to CH4/H2/Ar can enhance the InGaP etch rates at low flow rates, while at higher concentrations it provides an etch-stop reaction. The InGaP and AlInP etched under ECR conditions have somewhat rougher morphologies and different stoichiometries up to 200 Å from the sur face relative to the RIE samples. 相似文献
998.
Ogawa AK DeMattei JA Scarlato GR Tellew JE Chong LS Armstrong RW 《The Journal of organic chemistry》1996,61(18):6153-6161
We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product. 相似文献
999.
S. M. Fields R. C. Kong J. C. Fieldsted M. L. Lee P. A. Peaden 《Journal of separation science》1984,7(6):312-318
Fused silica capillary columns with internal diameters from 100 to 25 μm were coated with SE-54 and evaluated under supercritical fluid chromatographic conditions using carbon dioxide as mobile phase. Experimental results compared well with theoretical predictions. At ten times the optimum mobile phase velocity and for a capacity factor, k of 3, efficiencies of 2300 to 5600 plates m?1 were obtained for column diameters of 100 to 25 μm, respectively. 相似文献
1000.
Marumo A Kumazawa T Lee XP Fujimaki K Kuriki A Hasegawa C Sato K Seno H Suzuki O 《Journal of AOAC International》2005,88(6):1655-1660
Seven phenothiazine derivatives, perazine, perphenazine, prochlorperazine, propericiazine, thioproperazine, trifluoperazine, and flupentixol, have been found to be extractable from human plasma and urine samples using disk solid-phase extraction (SPE) with an Empore C18 cartridge. Human plasma and urine (1 mL each) containing the 7 phenothiazine derivatives were mixed with 2 mL of 0.1M NaOH and 7 mL distilled water and then poured into the disk SPE cartridges. The drugs were eluted with 1 mL chloroform- acetonitrile (8 + 2) and determined by liquid chromatography with ammonium formate/formic acid-acetonitrile gradient elution. The detection was performed by ultraviolet absorption at 250 nm. The separation of the 7 phenothiazine derivatives from each other and from impurities was generally satisfactory using a SymmetryShield RP8 column (150 x 2.1 mm id, 3.5 microm particle size). The recoveries of the 7 phenothiazine derivatives spiked into plasma and urine samples were 64.0-89.9% and 65.1-92.1%, respectively. Regression equations for the 7 phenothiazine derivatives showed excellent linearity, with detection limits of 0.021-0.30 microg/mL for plasma and 0.017-0.30 microg/mL for urine. The within-day and day-to-day coefficients of variation for both samples were commonly below 9.0 and 14.9%, respectively. 相似文献