全文获取类型
收费全文 | 107328篇 |
免费 | 1511篇 |
国内免费 | 586篇 |
专业分类
化学 | 44015篇 |
晶体学 | 1083篇 |
力学 | 7530篇 |
综合类 | 1篇 |
数学 | 34635篇 |
物理学 | 22161篇 |
出版年
2023年 | 160篇 |
2022年 | 464篇 |
2021年 | 663篇 |
2020年 | 526篇 |
2019年 | 562篇 |
2018年 | 10773篇 |
2017年 | 10567篇 |
2016年 | 6859篇 |
2015年 | 1599篇 |
2014年 | 1312篇 |
2013年 | 2131篇 |
2012年 | 5828篇 |
2011年 | 12723篇 |
2010年 | 7084篇 |
2009年 | 7262篇 |
2008年 | 8515篇 |
2007年 | 10416篇 |
2006年 | 2028篇 |
2005年 | 2829篇 |
2004年 | 2875篇 |
2003年 | 3121篇 |
2002年 | 2081篇 |
2001年 | 937篇 |
2000年 | 912篇 |
1999年 | 578篇 |
1998年 | 461篇 |
1997年 | 425篇 |
1996年 | 560篇 |
1995年 | 376篇 |
1994年 | 342篇 |
1993年 | 371篇 |
1992年 | 273篇 |
1991年 | 238篇 |
1990年 | 238篇 |
1989年 | 222篇 |
1988年 | 177篇 |
1987年 | 171篇 |
1986年 | 154篇 |
1985年 | 187篇 |
1984年 | 137篇 |
1983年 | 113篇 |
1982年 | 145篇 |
1981年 | 149篇 |
1980年 | 113篇 |
1979年 | 137篇 |
1978年 | 107篇 |
1977年 | 94篇 |
1976年 | 98篇 |
1975年 | 82篇 |
1973年 | 97篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
The second-order rate constants for the nucleophilic replacement of fluorine by isopropoxide in 5,6,7,8-tetrafluoro- and 6,7,-difluoro-1,2,3,4-tetrahydro-9-alkenyl-1,4-methanonaphthalenes and related 9-alkyl systems have been measured. A factor of 6 - 7 separates the most reactive compounds [the 9- (4′-trifluoromethylbenzylidene) derivatives] from the least reactive compounds [the syn-9-isopropyl derivatives] in both the tetrafluoro- and difluoro-series. It is concluded for these small reactivity differences. 相似文献
992.
Riehn C Matylitsky VV Jarzeba W Brutschy B Tarakeshwar P Kim KS 《Journal of the American Chemical Society》2003,125(52):16455-16462
In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes. 相似文献
993.
Jeong Gwi-Taek Park Don-Hee Hwang Baik Park Kyungmoon Kim Si-Wouk Woo Je-Chang 《Applied biochemistry and biotechnology》2002,98(1-9):1115-1127
The growth properties of Panax ginseng hairy roots transformed by Agrobacterium rhizogenes were compared between flask and aerated column or stirred bioreactor. In flask cultures, sucrose, initially 30 g/L, was nearly
exhausted after 45 d of culture. The pH of the medium dropped from 5.5 to 4.96 after 10 d, but afterward it gradually increased
to 6.4. After 45 d, hairy roots grew about 16-folds. The growth rate of hairy roots in air-bubble column or stirred bioreactor
cultures was 1.13 (1.11) to 1.23 (1.20) g fresh wt (dry wt)/(g of cells·d), respectively. For both bioreactors, growth was
about three times as high as in the flask cultivation. 相似文献
994.
The surface-enhanced Raman scatterings of dimethyl sulfide, diethyl sulfide and dimethyl disulfide have been investigated in silver sol. The dimethyl disulfide molecule decomposes on silver to the corresponding mercaptide implying facile cleavage of its S---S bond. The C---S bond in dialkyl monosulfide appears not to cleave on silver. For diethyl sulfide, the C2 conformation seems to be favorable on silver than other conformations. 相似文献
995.
G. Z. Kaziev A. A. Dutov S. I. Quinones A. de Ita S. N. Sychkin 《Russian Journal of General Chemistry》2005,75(1):18-20
Indium dodecatungstosilicate of the composition [In(OH)⋅5H2O]2 [SiW12O40]⋅H2O is synthesized and studied by means of IR spectroscopy, thermogravimetry, and X-ray phase analysis. The crystals of this compound are triclinic, space group P1, a 13.079(3), b 13.795(3), c 13.967(3) Å, α 90.08(3)°, β 103.76(3)°, ψ107.76(3)°, Z 2, and πcalc 4.900 g cm−3.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 21–23.Original Russian Text Copyright © 2005 by Kaziev, Dutov, Quinones, Ita, Sychkin. 相似文献
996.
Protein tyrosine phosphatase 1B (PTP1B) functions by removing the phosphoryl group from tyrosinephosphorylated proteins in
insulin signaling and metabolism. The regeneration of the active site involves a sulphenylamide intermediate derived from
the intrastrand cross-linking between the catalytic serine and the neighboring backbone nitrogen. Two mechanisms have been
proposed for the formation of the sulphenylamide intermediate and the subsequent reactivation of the catalytic site. In the
current work, the proposed mechanisms have been investigated by the use of density functional theory calculations. Our results
suggest that these two mechanisms have similar overall energy barriers and that the preferred route will be determined by
the availability of hydrogen peroxide or other oxidizing reagents. 相似文献
997.
Summary. A highly efficient, selective, fast, and cheap protocol is developed for oxidation of aromatic amines and alcohols utilizing
34% hydrogen peroxide in water catalyzed by some W- and Mo-based heteropolyoxometalates. Findings showed that dodecatungstophosphoric
acid, H3PW12O40, was the most efficient catalyst in the examined oxidation reactions. This methodology may prove to be a valuable alternative
for eco-friendly green oxidation. Inherent simplicity, easy work up, and using regenerable catalysts were other key aspects
of this oxidation protocol. 相似文献
998.
999.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
1000.
Muhammad Ilyas Sarwar Sonia Zulfiqar Zahoor Ahmad 《Colloid and polymer science》2007,285(15):1733-1739
Fluoro-aramid-based sol/gel-derived nanocomposites were synthesized by condensing a mixture of 4,4′-(hexafluoro-isopropylidene)dianiline
and 1,3-phenylenediamine with terephthaloylchloride (TPC) in dimethylacetamide. TPC was added in slight excess to produce
amide chains with carbonyl chloride end groups and then replaced with alkoxy groups using aminophenyltrimethoxysilane to develop
bonding with the silica network. Mechanical, dynamic mechanical thermal, water absorption and morphological measurements were
carried out on the thin hybrid films. Increase in the tensile strength and modulus was observed as compared to pristine polyamide.
The thermal decomposition temperature was found in the range of 400–500 °C. The water absorption was found to be reduced with
higher silica content. The glass transition temperature and the storage moduli increased with increasing silica concentration.
The maximum increase in the T
g value (345 °C) was observed with 20 wt% silica. Scanning electron microscopy revealed the uniform distribution of silica
in the matrix with an average particle size ranging from 8 to 50 nm. 相似文献