全文获取类型
收费全文 | 2142篇 |
免费 | 55篇 |
国内免费 | 15篇 |
专业分类
化学 | 1533篇 |
晶体学 | 12篇 |
力学 | 60篇 |
数学 | 355篇 |
物理学 | 252篇 |
出版年
2022年 | 21篇 |
2021年 | 34篇 |
2020年 | 22篇 |
2019年 | 25篇 |
2018年 | 25篇 |
2017年 | 17篇 |
2016年 | 32篇 |
2015年 | 55篇 |
2014年 | 42篇 |
2013年 | 110篇 |
2012年 | 119篇 |
2011年 | 137篇 |
2010年 | 76篇 |
2009年 | 61篇 |
2008年 | 107篇 |
2007年 | 111篇 |
2006年 | 126篇 |
2005年 | 89篇 |
2004年 | 90篇 |
2003年 | 80篇 |
2002年 | 65篇 |
2001年 | 39篇 |
2000年 | 20篇 |
1999年 | 13篇 |
1998年 | 20篇 |
1997年 | 17篇 |
1996年 | 35篇 |
1995年 | 19篇 |
1994年 | 18篇 |
1993年 | 28篇 |
1992年 | 14篇 |
1991年 | 23篇 |
1990年 | 19篇 |
1989年 | 19篇 |
1988年 | 21篇 |
1986年 | 13篇 |
1985年 | 28篇 |
1984年 | 24篇 |
1983年 | 14篇 |
1982年 | 27篇 |
1981年 | 26篇 |
1980年 | 15篇 |
1979年 | 32篇 |
1978年 | 20篇 |
1977年 | 28篇 |
1976年 | 22篇 |
1975年 | 23篇 |
1974年 | 24篇 |
1973年 | 18篇 |
1968年 | 12篇 |
排序方式: 共有2212条查询结果,搜索用时 15 毫秒
91.
G. Evan Boswell David L. Musso James L. Kelley Francis E. Soroko Barret R. Cooper 《Journal of heterocyclic chemistry》1996,33(1):33-39
A series of analogues of 2-phenylmorpholines with alkyl substituents at the C-3 position were synthesized for anti-tetrabenazine (anti-TBZ) testing in mice. The target compounds were prepared by reaction of (2-bromoalkyl) phenyl ketones 21a-h with the appropriate aminoalcohol 20a-b to form morpholinols 22a-h . Hydride reduction of the morpholinols gave aminodiols 23a-h which were cyclized to morpholines 6, 8, 10–12, 14–16, 18 and 19 by acid catalaysis. Compounds 7, 9, 13 and 17 were prepared by reductive formylation. The smaller straight chain substituents of 6, 8, 12 and 15 , and the beta branching of the iso-butyl group of 16 were well tolerated; anti-tetrabenazine ED50′s were comparable to compounds 2–5 . The α-branched, N-methylated, and side chain aryl derivatives were less active. 相似文献
92.
Buckley Crist Francis M. Mirabella 《Journal of Polymer Science.Polymer Physics》1999,37(21):3131-3140
Differential scanning calorimetry (DSC) can be used to infer the distribution of lamellar crystal thickness l. For homopolymers, the relation between melting temperature T and thickness is described by the Gibbs relation. In this case the weight distribution function of thickness g(l) ∝ P(T)(T − T)2, where P(T) is DSC power and T is the melting temperature of an infinitely thick crystal. Copolymer melting is affected by the concentration of noncrystallizable comonomer in the melt as well as lamellar thickness. Unknown melt composition in copolymers with nonequilibrium crystallinity makes determination of the correct distribution g(l) from DSC impossible. An approximate distribution g2(l) ∝ P(T)(T − T)2 is proposed, where T is based on Flory's equilibrium crystallization theory. This approximate distribution is most accurate when crystallinity is small, that is, near the upper end of the melting range. Results are reported for polyethylene homopolymer and model ethylene–butene random copolymers. Corrections were not made for distortion of the DSC endotherms by thermal lag or by melting and recrystallization; these experiments are primarily to illustrate the effect of analysis in terms of an incorrect g3(l) ∝ P(T). Average crystal thicknesses are about 20 nm for polyethylene and 5 nm for the copolymers. Distributions are characterized by lw /ln ≤ 1.1 in all cases. Width of the melting range is not a reliable indicator of the breadth of the thickness distribution. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3131–3140, 1999 相似文献
93.
94.
The PhSeBr-induced cyclization of N′-but-3-en-1-yl ethoxycarbonylhydrazines 1, phenylhydrazines 2 and dimethylhydrazines 3 has been studied. A 5-exo-trig ring closure occurred in each case and phenylselanylmethyl-pyrazolidines 4, 2-pyrazolines 5 and 10, 1-pyrazolines 8 and pyrazolidinium bromides 11 were synthesized. Radical deselenenylation has allowed the preparation of 5-methylpyrazolidines 12 and 5-methyl-2-pyrazolines 13 and 14. Decomposition of the dibromoselenuranes derived from 2-pyrazolines 5 and 10 afforded bromomethyl derivatives. With 1-phenyl-2-pyrazolines 10, an electrophilic p-halogenation of the phenyl nucleus was observed. 相似文献
95.
AymanA. Abdel‐Shafi PaulD. Beer RogerJ. Mortimer Francis Wilkinson 《Helvetica chimica acta》2001,84(9):2784-2795
Photophysical properties in dilute MeCN solution are reported for seven RuII complexes containing two 2,2′‐bipyridine (bpy) ligands and different third ligands, six of which contain a variety of 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridines, for one complex containing no 2,2′‐bipyridine, but 2 of these different ligands, for three multinuclear RuII complexes containing 2 or 4 [Ru(bpy)2] moieties and also coordinated via 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridine ligands, and for the complex [(Ru(bpy)2(L)]2+ where L is N,N′‐([2,2′‐bipyridine]‐4,4′‐diyl)bis[3‐methoxypropanamide]. Absorption maxima are red‐shifted with respect to [Ru(bpy)3]2+, as are phosphorescence maxima which vary from 622 to 656 nm. The lifetimes of the lowest excited triplet metal‐to‐ligand charge transfer states 3MLCT in de‐aerated MeCN are equal to or longer than for [Ru(bpy)3]2+ and vary considerably, i.e., from 0.86 to 1.71 μs. Rate constants kq for quenching by O2 of the 3MLCT states were measured and found to be well below diffusion‐controlled, ranging from 1.2 to 2.0⋅109 dm3 mol−1 s−1. The efficiencies f of singlet‐oxygen formation during oxygen quenching of these 3MLCT states are relatively high, namely 0.53 – 0.89. The product of kq and f gives the net rate constant k for quenching due to energy transfer to produce singlet oxygen, and kq−k equals k, the net rate constant for quenching due to energy dissipation of the excited 3MLCT states without energy transfer. The quenching rate constants were both found to correlate with ΔGCT, the free‐energy change for charge transfer from the excited Ru complex to oxygen, and the relative and absolute values of these rate constants are discussed. 相似文献
96.
Joseph I. Degraw Lawrence F. Kelly Roy L. Kisliuk Yvette Gaumont Francis M. Sirotnak 《Journal of heterocyclic chemistry》1982,19(6):1587-1588
A synthesis of 8,10-dideazaminopterin, using 2,4-diamino-6-bromomethyl-8-deazapteridine ( 2 ) as a key intermediate, is described. Condensation of the triphenylphosphinylide derived from 2 with p-formylbenzoyl-L-glutamate afforded a 9,10-dehydro-8,10-dideazaminopterin ester intermediate 5 . Hydrogenation of the olefinic linkage and subsequent hydrolysis of the glutamate ester gave the title compound. 8,10-Dideazaminopterin was a potent growth inhibitor of folate dependent bacteria. It was 16 times more potent then methotrexate as an inhibitor of dihydrofolate reductase derived from L1210 leukemia cells, and showed strong activity against L1210 in mice. 相似文献
97.
To establish the validity of the boundary-element method (BEM) for modeling scattering by swimbladder-bearing fish, the BEM is exercised in several ways. In a computation of backscattering by a 50-mm-diam spherical void in sea water at the four frequencies 38.1, 49.6, 68.4, and 120.4 kHz, agreement with the analytical solution is excellent. In computations of target strength as a function of tilt angle for each of 15 surface-adapted gadoids for which the swimbladders were earlier mapped, BEM results are in close agreement with Kirchhoff-approximation-model results at each of the same four frequencies. When averaged with respect to various tilt angle distributions and combined by regression analysis, the two models yield similar results. Comparisons with corresponding values derived from measured target strength functions of the same 15 gadoid specimens are fair, especially for the tilt angle distribution with the greatest standard deviation, namely 16 degrees. 相似文献
98.
Let ( G) be a flag-transitive c.c*-geometry whose point-stabilizer is not an affine group. We list all known examples and show that, if (, G) is a minimal unknown example, then G is an almost simple group and the commutator subgroup G is a simple group of Lie type. 相似文献
99.
Dr. Francis Buekenhout 《Mathematische Zeitschrift》1969,111(5):367-371
Sans résumé 相似文献
100.
Francis K. Fong 《Applied Physics A: Materials Science & Processing》1975,6(2):151-166
In this paper, the molecular details of the recently proposed energy upconversion theory of photosynthesis are reviewed. The primary light reactions are explained in terms of aC 2 symmetrical structure of the reaction center involving a (Chl?H2O)2 adduct. It is shown that exciton interaction within the (Chl?H2O)2 complex leads to an antisymmetric triplet state which may act as an energy trap. The presence of the energy trap in the reaction center suggests that the trigger step for the photoionization of active chlorophylls may involve the summation of two red excitation photons. Under normal conditions, the steadystate one-photon-per-electron quantum requirement is obtained. The functional properties of the various molecular constituents of the Chl-a molecule, such as the Ring V β-ketoester group, the phytyl tail, the central Mg atom, and the π-system of the macrocycle are explained within the present theoretical framework. A detailed analysis is given of the postulates and the consequences of the proposed model. The ramifications of the theory are probed, and their biological consequences are suggested for future study. 相似文献