全文获取类型
收费全文 | 97069篇 |
免费 | 1214篇 |
国内免费 | 474篇 |
专业分类
化学 | 37410篇 |
晶体学 | 909篇 |
力学 | 7171篇 |
数学 | 34675篇 |
物理学 | 18592篇 |
出版年
2023年 | 120篇 |
2022年 | 132篇 |
2021年 | 283篇 |
2020年 | 396篇 |
2019年 | 414篇 |
2018年 | 10574篇 |
2017年 | 10424篇 |
2016年 | 6624篇 |
2015年 | 1398篇 |
2014年 | 931篇 |
2013年 | 1357篇 |
2012年 | 4879篇 |
2011年 | 11690篇 |
2010年 | 6357篇 |
2009年 | 6663篇 |
2008年 | 7601篇 |
2007年 | 9730篇 |
2006年 | 1188篇 |
2005年 | 2194篇 |
2004年 | 2313篇 |
2003年 | 2606篇 |
2002年 | 1620篇 |
2001年 | 564篇 |
2000年 | 595篇 |
1999年 | 436篇 |
1998年 | 440篇 |
1997年 | 384篇 |
1996年 | 481篇 |
1995年 | 376篇 |
1994年 | 304篇 |
1993年 | 324篇 |
1992年 | 269篇 |
1991年 | 276篇 |
1990年 | 243篇 |
1989年 | 254篇 |
1988年 | 228篇 |
1987年 | 197篇 |
1986年 | 182篇 |
1985年 | 234篇 |
1984年 | 229篇 |
1983年 | 187篇 |
1982年 | 215篇 |
1981年 | 208篇 |
1980年 | 199篇 |
1979年 | 194篇 |
1978年 | 209篇 |
1977年 | 143篇 |
1976年 | 132篇 |
1975年 | 146篇 |
1973年 | 109篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
991.
Crystal Structure Determination of Ammonium catena-Polyphosphate II by X-Ray Powder Techniques The first structure determination of one of the five modifications of ammonium-catena-polyphosphate was performed using X-ray powder diffraction data. (NH4PO3)nII is formed by phase transformation of (NH4PO3)nI which on its part is obtained by condensation of NH4H2PO4 at 200°C in presence of urea. Modification II crystallizes in P212121 (a = 1 207.9(1), b = 648.87(8), c = 426.20(4) pm; Z = 4; 291 observed reflections; R(p) = 0.089; R(wp) = 0.111; R(I, hkl) = 0.088). The chain-anion runs parallel to the shortest axis, the period of identity is two. The ammonium ion is surrounded by a distorted tetrahedron of oxygen atoms (N? O-distances range from 285 to 292 pm, hydrogen bonds of middle strength). 相似文献
992.
Lee D Pervushin K Bischof D Braun M Thöny-Meyer L 《Journal of the American Chemical Society》2005,127(11):3716-3717
The heme chaperone CcmE is essential for the delivery of heme to c-type cytochromes. It forms an unusual transient, yet covalent, bond between an essential histidine, H130, and heme. We report on the discovery of the chemical structure of this bond solved by NMR, where the heme vinyl is cross-linked at the beta carbon to the Ndelta1 of H130. As this type of heme linkage has not been described previously in any cytochrome or hemoprotein, it represents a novel type of heme-histidine complex. 相似文献
993.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
994.
The conduction mechanism in microcrystalline cellulose (MCC) tablets at varying relative humidity (RH) has been investigated by using the techniques of low frequency dielectric spectroscopy and transient current analysis at room temperature. The dependence on RH on the measured conductivity and charge carrier density indicates that a high-power-law-exponent percolation process of cations being conducted on water molecules occupying available 6-OH units on the cellulose chains is the dominating dc conduction mechanism at RH below 3 wt % of moisture content. The experimentally observed decrease in charge carrier mobility with increasing moisture content shows that protons and H3O+ ions that are being blocked at empty 6-OH sites also contribute to the charge transport process in cellulose at low moisture contents. 相似文献
995.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
996.
PS-TEMPO, a polymer-supported 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), was successfully applied as a recyclable, active and selective catalyst for the oxidation of primary aliphatic and benzylic alcohols to aldehydes by molecular oxygen in the presence of Co(NO3)2 and Mn(NO3)2 as co-catalysts. 相似文献
997.
Dr. Alexandra R. McNeill Dr. Rodrigo Martinez-Gazoni Prof. Roger J. Reeves Prof. Martin W. Allen Prof. Alison J. Downard 《Chemphyschem》2021,22(13):1344-1351
ZnO is a strong candidate for transparent electronic devices due to its wide band gap and earth-abundance, yet its practical use is limited by its surface metallicity arising from a surface electron accumulation layer (SEAL). The SEAL forms by hydroxylation of the surface under normal atmospheric conditions, and is present at all crystal faces of ZnO, although with differing hydroxyl structures. Multilayer aryl films grafted from aryldiazonium salts have previously been shown to decrease the downward bending at O-polar ZnO thin films, with Zn−O−C bonds anchoring the aryl films to the substrate. Herein we show that the Zn-polar (0001), O-polar (000 ), and non-polar m-plane (10 0) faces of ZnO single crystals, can also be successfully electrografted with nitrophenyl (NP) films. In all cases, X-ray photoelectron spectroscopy (XPS) measurements reveal that the downward surface band bending decreases after modification. XPS provides strong evidence for Zn−O−C bonding at each face. Electrochemical reduction of NP films on O-polar ZnO single crystals converts the film to a mainly aminophenyl layer, although with negligible further change in band bending. This contrasts with the large upward shifts in band bending caused by X-ray induced reduction. 相似文献
998.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
999.
M. J. Musmar M. Robert Willcott Gary E. Martin Robert T. Gampe Masatomo Iwao Milton L. Lee Ralph E. Hurd Leroy F. Johnson Raymond N. Castle 《Journal of heterocyclic chemistry》1983,20(6):1661-1669
Development of successively higher field nmr spectrometers has facilitated the study of increasingly more complex molecules, although smaller molecules such as phenanthro[3,4-b]thiophene still offer very substantial assignment problems because of the highly congested nature of their 1H- and 13C-nmr spectra. Assignments of such spectra, if they are to be unequivocal, frequently require the utilization of two-dimensional nmr spectroscopic techniques. Total assignments of the 1H- and 13C-nmr spectra of phenanthro[3,4-b]thiophene are reported. Assignments were based on a conventional high resolution 500 MHz 1H-nmr spectrum, autocorrelated two-dimensional 1H-nmr spectra (COSY), two-dimensional 1H-13C chemical shift correlation spectra and a modified version of autocorrelated 13C-13C double quantum coherence two-dimensional nmr spectroscopy. From NOE measurements, a separation of 1.99 Å between H1 and H11 was computed, suggesting that phenanthro[3,4-b]thiophene has a pronounced helical conformation in solution. 相似文献
1000.
The versatile coordination chemistry of the well‐investigated phosphoraneiminato‐ligand R3PN— ( I ) was extended by the successive introduction of protons to the phosphorus atom. The position of the resulting equilibrium between the NH‐phosphanylamido‐ [R2P‐NH—] and the PH‐phosphoraneiminato‐form [R2HP=N—] is affected by the Lewis acidity of the coordinated metal fragment. Experimental studies on complexes with various substitution patterns at the group 4 metal center R2HP=N[M] ( II ) were unambiguously confirmed by DFT‐calculations. The isolation of group 4 PH‐dihydrido‐phosphoraneiminato‐complexes RH2P‐N[M] ( III ) is prevented by the low thermodynamic stability of the target molecules, also supported by the results of ab initio calculations. However, an access to the by then unknown transition‐metal substituted iminophosphanes RP=N[M] ( IV ) was verified for the first time. Within extensive studies on the coordination chemistry of bis(imino)phosphoranes RP(=NR′)(=NR″), several species of group 4 complexes R(R′N=)P=N[M] ( V ) were isolated and structurally characterized. In this case, investigations on the NH/PH‐tautomerism were performed exclusively on theoretical level, because the required educts are experimentally non‐accessible due to their kinetic instability. 相似文献