全文获取类型
收费全文 | 104889篇 |
免费 | 1130篇 |
国内免费 | 602篇 |
专业分类
化学 | 42751篇 |
晶体学 | 900篇 |
力学 | 7285篇 |
综合类 | 1篇 |
数学 | 36967篇 |
物理学 | 18717篇 |
出版年
2021年 | 274篇 |
2020年 | 346篇 |
2019年 | 314篇 |
2018年 | 10617篇 |
2017年 | 10458篇 |
2016年 | 6601篇 |
2015年 | 1440篇 |
2014年 | 936篇 |
2013年 | 1698篇 |
2012年 | 5125篇 |
2011年 | 12061篇 |
2010年 | 6514篇 |
2009年 | 6772篇 |
2008年 | 7930篇 |
2007年 | 10072篇 |
2006年 | 1750篇 |
2005年 | 2667篇 |
2004年 | 2819篇 |
2003年 | 3026篇 |
2002年 | 2028篇 |
2001年 | 691篇 |
2000年 | 688篇 |
1999年 | 544篇 |
1998年 | 571篇 |
1997年 | 574篇 |
1996年 | 589篇 |
1995年 | 472篇 |
1994年 | 462篇 |
1993年 | 435篇 |
1992年 | 369篇 |
1991年 | 382篇 |
1990年 | 323篇 |
1989年 | 329篇 |
1988年 | 308篇 |
1987年 | 264篇 |
1986年 | 291篇 |
1985年 | 395篇 |
1984年 | 407篇 |
1983年 | 338篇 |
1982年 | 378篇 |
1981年 | 345篇 |
1980年 | 381篇 |
1979年 | 313篇 |
1978年 | 331篇 |
1977年 | 294篇 |
1976年 | 239篇 |
1975年 | 204篇 |
1974年 | 203篇 |
1973年 | 186篇 |
1972年 | 127篇 |
排序方式: 共有10000条查询结果,搜索用时 371 毫秒
961.
Ian K. Boddy J. Boniface Richard C. Cambie Peter A. Craw David S. Larsen Hamish McDonald Peter S. Rutledge Paul D. Woodgate 《Tetrahedron letters》1982,23(42):4407-4408
Gentle heating of allyloxyanthraquinones with sodium dithionite in dimethylformanide - water effects a rapid and controlled rearrangement to give high yields of 2-allyanthraquinones. 相似文献
962.
Anzalone PW Baru AR Danielson EM Hayes PD Nguyen MP Panico AF Smith RC Mohan RS 《The Journal of organic chemistry》2005,70(6):2091-2096
[reaction: see text] Three one-pot methods for the conversion of aldehydes to homoallyl ethers catalyzed by Bi(OTf)(3).xH(2)O (1 < x < 4) have been developed. The one-pot synthesis of homoallyl ethers can be achieved either by in situ generation of the acetal followed by its reaction with allyltrialkylsilane or by a three-component synthesis in which the aldehyde, trimethylorthoformate or an alkoxytrimethylsilane and allyltrimethylsilane are mixed together in the presence of bismuth triflate (0.1-1.0 mol %). In addition, a three-component synthesis of homoallyl acetates, which is achieved by reacting the aldehyde, acetic anhydride, and allyltrimethylsilane in the presence of bismuth triflate (3.0-5.0 mol %), has been developed. The use of a relatively nontoxic, easy to handle, and inexpensive catalyst adds to the versatility of these methods. 相似文献
963.
Dariush Habibollahzadeh Jane S. Murray Michael Grodzicki Jorge M. Seminario Peter Politzer 《International journal of quantum chemistry》1992,42(2):267-272
The C? H bond dissociation energy of acetylene was computed by both ab initio approaches and density functional theory in a local density approximation (DFT–LDA ). Structures and energies for acetylene and its dissociation products (the ethynyl and hydrogen radicals) are presented and compared. Using directly computed HCCH and HCC· energies and the exact H· value, the DFT–LDA calculations are found to yield C? H dissociation energies ranging from 129 to 131 kcal/mol, in good agreement with recent experimental and the highest level theoretical results. The DFT–LDA results show little dependence upon the computational procedure used to obtain geometries. 相似文献
964.
Two hydrated uranyl arsenates, Cs2(UO2)[(UO2)(AsO4)]4(H2O)2 (CsUAs) and Rb2(UO2)[(UO2)(AsO4)]4(H2O)4.5 (RbUAs), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα radiation and a CCD-based area detector. The crystal structure of RbUAs was solved by direct methods, whereas the structure model of the phosphate Cs2(UO2)[(UO2)(PO4)]4(H2O)2 was used for CsUAs; both were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (CsUAs, RbUAs) wR2=0.061,0.041, for all data, and R1=0.032,0.021, calculated for 5098, 4991 unique observed reflections (|Fo|>4σF), respectively. The compound CsUAs is orthorhombic, space group Cmc21, Z=4, a=15.157(2), b=14.079(2), c=13.439(2) Å, V=2867.9(1) Å3. RbUAs is monoclinic, space group C2/m, Z=4, a=13.4619(4), b=15.8463(5), c=14.0068(4) Å, β=92.311(1)°, V=2985.52(2) Å3. The structures consist of sheets of arsenate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(AsO4)]−, that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two arsenate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. CsUAs is isostructural with its phosphate analogue, and has two Cs atoms and a H2O group in its structural cavities. RbUAs is not isostructural with its phosphate analogue, although it has a homeotypic framework. Its structural cavities are occupied by three Rb atoms and four H2O groups; one Rb position and three of the interstitial H2O groups are half-occupied. The partial occupancies of these positions probably result from the accommodation of the larger As atoms (relative to P) in the framework and resultant larger cavities. 相似文献
965.
Pyrolysis of homoadamant-3-ene (), generated from 1-adamantylcarbene (), leads to the same three olefins (, , and ) that are produced from pyrolysis of 3-homoadamantyl acetate (). 相似文献
966.
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
967.
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
968.
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
969.
970.
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