全文获取类型
收费全文 | 16153篇 |
免费 | 816篇 |
国内免费 | 197篇 |
专业分类
化学 | 11576篇 |
晶体学 | 125篇 |
力学 | 861篇 |
综合类 | 3篇 |
数学 | 1936篇 |
物理学 | 2665篇 |
出版年
2024年 | 29篇 |
2023年 | 129篇 |
2022年 | 438篇 |
2021年 | 738篇 |
2020年 | 659篇 |
2019年 | 724篇 |
2018年 | 760篇 |
2017年 | 678篇 |
2016年 | 1004篇 |
2015年 | 691篇 |
2014年 | 949篇 |
2013年 | 1696篇 |
2012年 | 1323篇 |
2011年 | 1221篇 |
2010年 | 842篇 |
2009年 | 741篇 |
2008年 | 781篇 |
2007年 | 687篇 |
2006年 | 490篇 |
2005年 | 463篇 |
2004年 | 302篇 |
2003年 | 285篇 |
2002年 | 232篇 |
2001年 | 109篇 |
2000年 | 71篇 |
1999年 | 90篇 |
1998年 | 57篇 |
1997年 | 71篇 |
1996年 | 67篇 |
1995年 | 44篇 |
1994年 | 52篇 |
1993年 | 27篇 |
1992年 | 47篇 |
1991年 | 43篇 |
1990年 | 39篇 |
1989年 | 43篇 |
1988年 | 37篇 |
1987年 | 46篇 |
1986年 | 33篇 |
1985年 | 49篇 |
1984年 | 47篇 |
1983年 | 24篇 |
1982年 | 41篇 |
1981年 | 26篇 |
1980年 | 37篇 |
1979年 | 26篇 |
1978年 | 24篇 |
1977年 | 17篇 |
1976年 | 20篇 |
1974年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
821.
Dennis Cao Dr. Michal Juríček Zachary J. Brown Dr. Andrew C.‐H. Sue Dr. Zhichang Liu Juying Lei Anthea K. Blackburn Dr. Sergio Grunder Dr. Amy A. Sarjeant Prof. Ali Coskun Prof. Cheng Wang Prof. Omar K. Farha Prof. Joseph T. Hupp Prof. J. Fraser Stoddart 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8457-8465
We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC4+) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC4+ rings comprise either 1) two bipyridinium (BIPY2+) units or 2) a BIPY2+ and a diazapyrenium (DAP2+) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO3)2?2.5 H2O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY2+ units by a DAP2+ unit: only the translational isomer in which the DAP2+ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures. 相似文献
822.
Switching adaptive controllers to control fractional‐order complex systems with unknown structure and input nonlinearities 下载免费PDF全文
This article investigates the chaos control problem for the fractional‐order chaotic systems containing unknown structure and input nonlinearities. Two types of nonlinearity in the control input are considered. In the first case, a general continuous nonlinearity input is supposed in the controller, and in the second case, the unknown dead‐zone input is included. In each case, a proper switching adaptive controller is introduced to stabilize the fractional‐order chaotic system in the presence of unknown parameters and uncertainties. The control methods are designed based on the boundedness property of the chaotic system's states, where, in the proposed methods the nonlinear/linear dynamic terms of the fractional‐order chaotic systems are assumed to be fully unknown. The analytical results of the mentioned techniques are proved by the stability analysis theorem of fractional‐order systems and the adaptive control method. In addition, as an application of the proposed methods, single input adaptive controllers are adopted for control of a class of three‐dimensional nonlinear fractional‐order chaotic systems. And finally, some numerical examples illustrate the correctness of the analytical results. © 2014 Wiley Periodicals, Inc. Complexity 21: 211–223, 2015 相似文献
823.
An easy and mild approach using ultrasound-assisted reaction addition of alcohols to N-acyliminium ion mediated by Lewis acid, In(OTf)3, allowed the synthesis of ether pyrrolidinones; next, the products were converted to 1,2,3-triazoles using click chemistry reaction conditions. The products in both reactions were afforded in moderate to good yields. 相似文献
824.
A high yielding method for 1,2-cis-β-D-mannosylation by intra-molecular aglycon delivery (IAD) through p-methoxy benzyl ether/acetal exchange and phenylsulfoxide donor is reported, along with its application in iterative assembly of antigenic (1 → 2)-β-pentamannoside domain of phospholipomannan (PLM) of fungal pathogen Candida albicans. 相似文献
825.
826.
We report here the synthesis of a nanopolymer-supported palladium(II) complex catalyst, [PS-tet-Pd(II)] using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR, and energy dispersive X-ray spectroscopy (EDS). PS-tet-Pd(II) proves to be a useful heterogeneous catalyst in the copper- and phosphine-free Sonogashira coupling reaction in water. The catalyst can be recovered from the reaction mixture by simple filtration and reused several times without any significant loss of catalytic activity. 相似文献
827.
Ahmed M. Metwaly Frank R. Fronczek Guoyi Ma Hazem A. Kadry Atef A. El-Hela Abd-Elsalam I. Mohammad Stephen J. Cutler Samir A. Ross 《Tetrahedron letters》2014
Four new (1–4) and two known (5 and 6) α-pyrone derivatives have been isolated from Alternaria phragmospora, an endophytic fungus from Vinca rosea, leaves. The isolated compounds were chemically identified to be 5-butyl-4-methoxy-6-methyl-2H-pyran-2-one (1), 5-butyl-6-(hydroxymethyl)-4-methoxy-2H-pyran-2-one (2), 5-(1-hydroxybutyl)-4-methoxy-6-methyl-2H-pyran-2-one (3), 4-methoxy-6-methyl-5-(3-oxobutyl)-2H-pyran-2-one (4), 5-(2-hydroxyethyl)-4-methoxy-6-methyl-2H-pyran-2-one (5), and 5-[(2E)-but-2-en-1-yl]-4-methoxy-6-methyl-2H-pyran-2-one (6). Compounds 2 and 4 showed moderate antileukemic activities against HL60 cells with IC50 values of 2.2 and 0.9 μM and against K562 cells with IC50 values of 4.5 and 1.5 μM, respectively. 相似文献
828.
A new method is applied to prepare stable aqueous dispersion of magnetic iron oxide nanoparticles (MNPs) by biocompatible maleate polymers. Fe3O4 magnetic core–shell nanoparticles are obtained via forming an inclusion complex between carboxylic acid groups of maleated biocompatible polymers shell and Fe3O4 MNPs core surface. Maleate polymers are synthesized via esterification of poly(ethylene glycol), poly(vinyl alcohol) and starch with maleic anhydride (MA). The Fe3O4 magnetic core–shell nanoparticles are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The obtained magnetic core–shell nanoparticles exhibit superparamagnetic property and reveal long‐term aqueous stability. This work represents a valid methodology to produce highly stable aqueous dispersion of Fe3O4 MNPs ferrofluids which can be expected to have great potential as contrast agent for magnetic resonance imaging. Furthermore, the shell composition of biocompatible maleate polymers with double bond of MA as crosslinker agent allows the polymerization with other monomers to design preferred drug delivery systems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
829.
The densities, ρ, refractive indices, n D, and ultrasonic speeds, u, of binary mixtures of acetonitrile (AN) with poly(ethylene glycol) 200 (PEG200), poly(ethylene glycol) 300 (PEG300) and poly(ethylene glycol) 400 (PEG400) were measured over the entire composition range at temperatures (298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. From the experimental data, the excess molar volumes, \( V_{\text{m}}^{\text{E}} \) , deviations in refractive indices, \( \Delta n_{\text{D}} \) , excess molar isentropic compressibility, \( K_{{s , {\text{m}}}}^{\text{E}} \) , excess intermolecular free length, \( L_{\text{f}}^{\text{E}} \) , and excess acoustic impedance, Z E, have been evaluated. The partial molar volumes, \( \overline{V}_{\text{m,1}} \) and \( \overline{V}_{\text{m,2}} \) , partial molar isentropic compressibilities, \( \overline{K}_{{s , {\text{m,1}}}} \) and \( \overline{K}_{{s , {\text{m,2}}}} \) , and their excess values over whole composition range and at infinite dilution have also been calculated. The variations of these properties with composition and temperature are discussed in terms of intermolecular interactions in these mixtures. The results indicate the presence of specific interactions among the AN and PEG molecules, which follow the order PEG200 < PEG300 < PEG400. 相似文献
830.
A mixture of bismuth nitrate pentahydrate and potassium aryltrifluoroborate in toluene under microwave heating at 120 °C for 20 min provides an interesting and mild reaction protocol for the synthesis of aryl nitrite. The conversion to aryl nitrites from aryltrifluoroborates without transition metal catalyst and base in high yields is remarkable. 相似文献