全文获取类型
收费全文 | 65461篇 |
免费 | 10144篇 |
国内免费 | 2318篇 |
专业分类
化学 | 61391篇 |
晶体学 | 906篇 |
力学 | 1699篇 |
综合类 | 35篇 |
数学 | 7763篇 |
物理学 | 6129篇 |
出版年
2023年 | 37篇 |
2022年 | 104篇 |
2021年 | 317篇 |
2020年 | 680篇 |
2019年 | 2487篇 |
2018年 | 2364篇 |
2017年 | 2766篇 |
2016年 | 3051篇 |
2015年 | 5359篇 |
2014年 | 5101篇 |
2013年 | 7239篇 |
2012年 | 5598篇 |
2011年 | 5272篇 |
2010年 | 4318篇 |
2009年 | 4173篇 |
2008年 | 4563篇 |
2007年 | 3907篇 |
2006年 | 3579篇 |
2005年 | 3347篇 |
2004年 | 2743篇 |
2003年 | 2547篇 |
2002年 | 3236篇 |
2001年 | 1672篇 |
2000年 | 1559篇 |
1999年 | 740篇 |
1998年 | 176篇 |
1997年 | 92篇 |
1996年 | 72篇 |
1995年 | 62篇 |
1994年 | 71篇 |
1993年 | 48篇 |
1992年 | 54篇 |
1991年 | 48篇 |
1990年 | 48篇 |
1989年 | 49篇 |
1988年 | 35篇 |
1987年 | 55篇 |
1986年 | 29篇 |
1985年 | 58篇 |
1984年 | 40篇 |
1983年 | 26篇 |
1982年 | 37篇 |
1981年 | 14篇 |
1980年 | 20篇 |
1979年 | 28篇 |
1978年 | 15篇 |
1977年 | 22篇 |
1976年 | 16篇 |
1974年 | 11篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
1.
2.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
3.
4.
5.
6.
5‐Amino‐4‐methyl‐2‐phenyl‐6‐substitutedfuro[2,3‐d]pyrimidines ( 2a‐c ) were reacted with 2,5‐dimethoxytetrahydrfuran to afford the pyrrolyl derivatives 3a‐c . Compound 3a was chosen as intermediate for the synthesis of poly fused heterocycles incorporated furopyrimidines moiety 4–11 . Some of the synthesized compounds were screened for their antibacterial and antifungal activities. 相似文献
7.
Let G=(V(G),E(G)) be a graph. A (n,G, λ)‐GD is a partition of the edges of λKn into subgraphs (G‐blocks), each of which is isomorphic to G. The (n,G,λ)‐GD is named as graph design for G or G‐decomposition. The large set of (n,G,λ)‐GD is denoted by (n,G,λ)‐LGD. In this work, we obtain the existence spectrum of (n,P3,λ)‐LGD. © 2002 Wiley Periodicals, Inc. J Combin Designs 10: 151–159, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10008 相似文献
8.
Several new families of c‐Bhaskar Rao designs with block size 4 are constructed. The necessary conditions for the existence of a c‐BRD (υ,4,λ) are that: (1)λmin=?λ/3 ≤ c ≤ λ and (2a) c≡λ (mod 2), if υ > 4 or (2b) c≡ λ (mod 4), if υ = 4 or (2c) c≠ λ ? 2, if υ = 5. It is proved that these conditions are necessary, and are sufficient for most pairs of c and λ; in particular, they are sufficient whenever λ?c ≠ 2 for c > 0 and whenever c ? λmin≠ 2 for c < 0. For c < 0, the necessary conditions are sufficient for υ> 101; for the classic Bhaskar Rao designs, i.e., c = 0, we show the necessary conditions are sufficient with the possible exception of 0‐BRD (υ,4,2)'s for υ≡ 4 (mod 6). © 2002 Wiley Periodicals, Inc. J Combin Designs 10: 361–386, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10009 相似文献
9.
LYNDA D. RODWELL EDWARD B. BARBIER CALLUM M. ROBERTS TIM R. McCLANAHAN 《Natural Resource Modeling》2002,15(4):453-486
ABSTRACT. The excessive and unsustainable exploitation of our marine resources has led to the promotion of marine reserves as a fisheries management tool. Marine reserves, areas in which fishing is restricted or prohibited, can offer opportunities for the recovery of exploited stock and fishery enhancement. In this paper we examine the contribution of fully protected tropical marine reserves to fishery enhancement by modeling marine reserve‐fishery linkages. The consequences of reserve establishment on the long‐run equilibrium fish biomass and fishery catch levels are evaluated. In contrast to earlier models this study highlights the roles of both adult (and juvenile) fish migration and larval dispersal between the reserve and fishing grounds by employing a spawner‐recruit model. Uniform larval dispersal, uniform larval retention and complete larval retention combined with zero, moderate and high fish migration scenarios are analyzed in turn. The numerical simulations are based on Mombasa Marine National Park, Kenya, a fully protected coral reef marine reserve comprising approximately 30% of former fishing grounds. Simulation results suggest that the establishment of a fully protected marine reserve will always lead to an increase in total fish biomass. If the fishery is moderately to heavily exploited, total fishery catch will be greater with the reserve in all scenarios of fish and larval movement. If the fishery faces low levels of exploitation, catches can be optimized without a reserve but with controlled fishing effort. With high fish migration from the reserve, catches are optimized with the reserve. The optimal area of the marine reserve depends on the exploitation rate in the neighboring fishing grounds. For example, if exploitation is maintained at 40%, the ‘optimal’ reserve size would be 10%. If the rate increases to 50%, then the reserve needs to be 30% of the management area in order to maximize catches. However, even in lower exploitation fisheries (below 40%), a small reserve (up to 20%) provides significantly higher gains in fish biomass than losses in catch. Marine reserves are a valuable fisheries management tool. To achieve maximum fishery benefits they should be complemented by fishing effort controls. 相似文献
10.
We investigate the conjecture that every circulant graph X admits a k‐isofactorization for every k dividing |E(X)|. We obtain partial results with an emphasis on small values of k. © 2006 Wiley Periodicals, Inc. J Combin Designs 14: 406–414, 2006 相似文献