全文获取类型
收费全文 | 3814篇 |
免费 | 140篇 |
国内免费 | 45篇 |
专业分类
化学 | 2513篇 |
晶体学 | 28篇 |
力学 | 135篇 |
综合类 | 2篇 |
数学 | 563篇 |
物理学 | 758篇 |
出版年
2023年 | 25篇 |
2022年 | 30篇 |
2021年 | 52篇 |
2020年 | 50篇 |
2019年 | 43篇 |
2018年 | 43篇 |
2017年 | 21篇 |
2016年 | 75篇 |
2015年 | 69篇 |
2014年 | 96篇 |
2013年 | 193篇 |
2012年 | 253篇 |
2011年 | 268篇 |
2010年 | 139篇 |
2009年 | 142篇 |
2008年 | 231篇 |
2007年 | 220篇 |
2006年 | 221篇 |
2005年 | 192篇 |
2004年 | 173篇 |
2003年 | 150篇 |
2002年 | 112篇 |
2001年 | 94篇 |
2000年 | 97篇 |
1999年 | 58篇 |
1998年 | 56篇 |
1997年 | 34篇 |
1996年 | 74篇 |
1995年 | 52篇 |
1994年 | 51篇 |
1993年 | 46篇 |
1992年 | 43篇 |
1991年 | 37篇 |
1990年 | 28篇 |
1989年 | 22篇 |
1988年 | 27篇 |
1987年 | 24篇 |
1986年 | 20篇 |
1985年 | 47篇 |
1984年 | 29篇 |
1983年 | 29篇 |
1982年 | 25篇 |
1981年 | 38篇 |
1980年 | 29篇 |
1979年 | 25篇 |
1978年 | 30篇 |
1977年 | 27篇 |
1976年 | 20篇 |
1975年 | 25篇 |
1974年 | 37篇 |
排序方式: 共有3999条查询结果,搜索用时 343 毫秒
131.
Abstract. New results are presented on the effects of mono- and divalent cations on concurrent changes in the microsecond yields and kinetics of chlorophyll a fluorescence and delayed light emission, and the light saturation curve for the latter at 100 μs, following a 10 ns flash at 337 nm. (1) The fluorescence yield increases exponentially from 3 to 30 μs (lifetime, τ, 6.4 ± 0.6/μs), and decays biphasically between 50 and 800μs. (2) The delayed light emission decays biphasically with two exponential phases: fast phase, T= 7–10μs, and slow phase, T= 33–40μs. (3) The light saturation curve for 100μs delayed light emission is satisfactorily represented by a one-hit Poisson saturation curve. (4) Addition of 5 mM NaCl to salt-depleted chloroplasts decreases (by as much as 40%) the yields of μs fluorescence and delayed light emission, and the subsequent addition of 5mM MgCl2 increases the yields (≤2 × over samples with only NaCl). (5) The fluorescence yield rise and delayed light emission decay kinetics are independent of low concentrations of cations. The lifetime of the fast phase of fluorescence decay changes from ?90μs to ?160μs, when Na+ or Na++ Mg2+ are added. Based on a detailed analysis presented in this paper, the following conclusions regarding the effects of low concentrations (few mM) of mono-and divalent cations in sucrose-washed chloroplasts at room temperature are made: (a) Na+ decreases (?6%) and Mg2+ increases (? 20% compared with the Na+ sample) the sensitization of photosystem II photochemistry: this effect is small, but significant. (b) Na+ increases and Mg2+ decreases the efficiency for radiationless transitions in singlet excited Chl a in the antenna and closed reaction center of PS II; this includes non-radiative energy transfer to PS I, intramolecular intersystem crossing and internal conversion. The ratio of the sum of the rate constants for radiationless transitions to that for fluorescence increases by ? 2-fold upon the addition of Na+, and is completely reversed by the addition of Mg2+. (c) The rate constant for the re-oxidation of Q- decreases (about 50%) in the presence of Na+ or Na++ Mg2+. These conclusions imply that cations produce multiple changes in the primary photoprocesses of PS II at physiological temperatures. It is proposed that these changes are mutually independent and can co-exist. 相似文献
132.
Yeung WF Lau PH Lau TC Wei HY Sun HL Gao S Chen ZD Wong WT 《Inorganic chemistry》2005,44(19):6579-6590
The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N'-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}.6CH3OH.2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn(II) and Ru(III) centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2.H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}.2CH3OH.2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru(III) and M(II) (Mn(II), Ni(II)) ions. 相似文献
133.
A series of new C2-symmetric 2,2′-bipyridine-contaning crown macrocycles 1-4 has been developed for enantiomeric recognition of amino acid derivatives. These new macrocycles have been showed to be strong complexing agents for primary organic ammonium salts (with K up to 4.83×105 M−1 and −ΔG0 up to 32.4 kJ mol−1) and also useful chromophores for UV-vis titration studies. These macrocyclic hosts exhibited enantioselective binding towards the (S)-enantiomer of phenylglycine methyl ester hydrochloride (Am1) with K(S)/K(R) up to 2.10 (ΔΔG0=−1.84 kJ mol−1) in CH2Cl2 with 0.25% CH3OH. The structure-binding relationship studies showed that the aromatic subunit and the ester group of the ammonium guests are both important for good enantioselectivity. In addition, the host-guest complexes have been studied using various NMR experiments. 相似文献
134.
Reactions of coordinatively unsaturated Ru[N(Ph2PQ)2]2(PPh3) (Q = S (1), Se (2)) with pyridine (py), SO2, and NH3 afford the corresponding 18e adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH3 (5); Q = Se, L = py (3), SO2 (4), NH3 (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh3 occupying the apical position, while that in 6 is pseudooctahedral with PPh3 and NH3 mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) A, respectively. The Ru-N bond length in 6 is 2.185(3) A. Treatment of 1 or 2 with substituted hydrazines L or NH2OH yields the respective adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH2NH2 (12), t-BuNHNH2 (14), l-aminopiperidine (C5H10NNH2) (15); Q = Se, L = PhCONHNH2 (7), PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2 (11), NH2NH2 (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh3 and hydrazine mutually cis. The Ru-N bond lengths in cis-14.CH2Cl2 and cis-15 are 2.152(3) and 2.101(3) A, respectively. The Ru-N-N bond angles in cis-14.CH2Cl2 and cis-15 are 120.5(4) and 129.0(2) degrees, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16), which are characterized by mass spectrometry, 1H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH3 and H2O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) A, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied. 相似文献
135.
K. P. Sivaramakrishnan C. Samyn Ira John Westerman Daniel Ting-Man Wong C. S. Marvel 《Journal of polymer science. Part A, Polymer chemistry》1975,13(5):1083-1094
1,3-Bis(p-phenoxybenzenesulfonyl)benzene, 4,4′-bis(p-phenoxybenzenesulfonyl)diphenyl ether, and 4,4′-diphenoxydiphenyl sulfone were polymerized with isophthaloyl or terephthaloyl chlorides in Friedel-Crafts type polymerizations. These polymers had [2,2]p-cyclophane units in the backbone, introduced by employing 3,9-bis(p-phenoxybenzoyl) [2.2]p-cyclophane as part of the polyaryl ether component. Thermolysis of the dimethylene bridge of the [2.2]p-cyclophane monomer produced diradicals which combined across polymer chains to provide crosslinks. p-Cyclophane polymers with 1,3-bis-(p-phenoxybenzenesulfonyl)benzene showed potential as high performance, thermally stable laminating resins. 相似文献
136.
The quaternion algebraB[j] over a commutative ringB with 1 defined byS. Parimala andR. Sridharan is generalized in two directions: (1) the ringB may be non-commutative with 1, and (2)j
2 may be any invertible element (not necessarily –1). LetG={} be an automorphism group ofB of order 2, andA={b inB| (b)=b}. LetB[j] be a generalized quaternion algebra such thataj (a) for eacha inB. It will be shown thatB is Galois (for non-commutative ring extensions) overA which is contained in the center ofB if and only ifB[j] is Azumaya overA. Also,A[j] is a splitting ring forB[j] such thatA[j] is Galois overA. Moreover, we shall determine which automorphism group ofA[j] is a Galois group. 相似文献
137.
Man-Kit Lau Qian-Feng Zhang Wing-Tak Wong Wa-Hung Leung 《Journal of organometallic chemistry》2004,689(14):2401-2410
Treatment of [M(Buppy)2Cl]2 (M=Ir (1), Rh (2); BuppyH=2-(4′-tert-butylphenyl)pyridine) with Na(Et2NCS2), K[S2P(OMe)2], and K[N(Ph2PS)2]2 afforded monomeric [Ir(Buppy)2(S∧S)] (S∧S=Et2NCS2 (3), S2P(OMe)2 (4), N(PPh2S)2 (5)) and [Rh(Buppy)2(S∧S)] (S∧S=Et2NCS2 (6), S2P(OMe)2 (7), N(PPh2S)2 (8)), respectively. Reaction of 1 with Na[N(PPh2Se)2] gave [Ir(Buppy)2{N(PPh2Se)2}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)2}2(μ-SCN)2] (M=Ir (10), Rh (11)), in which the SCN− ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et4N]2[WQ4] gave trinuclear heterometallic complexes [{Ir(Buppy)2}2(μ-WQ4)] (Q=S (12), Se (13)) and [{Rh(Buppy)2}2{(μ-WQ)4}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)2}2{W(O)(μ-S)2(μ3-S)}] (16) that has been characterized by X-ray diffraction. 相似文献
138.
139.
Synthetic organic chemists are continually looking for milder, more specific methods of effecting given transformations, and one such problem which recently arose in our laboratory involved ester cleavage. In particular, we sought a specific, wild, non-hydrolytic method for effecting teh ester - acid transformation under conditions which other acid or base sensitive functional groups would survive. 相似文献
140.
A k-regular bipartite graph is said to be 2-factor hamiltonian if each of its 2-factor is hamiltonian. It is well known that if a k-regular bipartite graph is 2-factor hamiltonian, then k?Q3. In this paper, we give a new proof of this fact. 相似文献