全文获取类型
收费全文 | 39341篇 |
免费 | 5658篇 |
国内免费 | 4893篇 |
专业分类
化学 | 29041篇 |
晶体学 | 594篇 |
力学 | 1804篇 |
综合类 | 366篇 |
数学 | 4522篇 |
物理学 | 13565篇 |
出版年
2024年 | 79篇 |
2023年 | 628篇 |
2022年 | 840篇 |
2021年 | 1186篇 |
2020年 | 1383篇 |
2019年 | 1452篇 |
2018年 | 1185篇 |
2017年 | 1264篇 |
2016年 | 1682篇 |
2015年 | 1728篇 |
2014年 | 2157篇 |
2013年 | 2808篇 |
2012年 | 3387篇 |
2011年 | 3637篇 |
2010年 | 2675篇 |
2009年 | 2574篇 |
2008年 | 2762篇 |
2007年 | 2585篇 |
2006年 | 2393篇 |
2005年 | 1968篇 |
2004年 | 1567篇 |
2003年 | 1286篇 |
2002年 | 1231篇 |
2001年 | 1031篇 |
2000年 | 884篇 |
1999年 | 728篇 |
1998年 | 545篇 |
1997年 | 471篇 |
1996年 | 465篇 |
1995年 | 399篇 |
1994年 | 395篇 |
1993年 | 297篇 |
1992年 | 273篇 |
1991年 | 237篇 |
1990年 | 234篇 |
1989年 | 178篇 |
1988年 | 161篇 |
1987年 | 116篇 |
1986年 | 136篇 |
1985年 | 143篇 |
1984年 | 86篇 |
1983年 | 88篇 |
1982年 | 66篇 |
1981年 | 53篇 |
1980年 | 54篇 |
1979年 | 43篇 |
1977年 | 39篇 |
1976年 | 38篇 |
1974年 | 49篇 |
1973年 | 46篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
991.
We report the time courses of five solid-phase reactions obtained using single bead FTIR microspectroscopy. This time-resolved information aided in the determination of the required reaction time, the nature of the solid-phase reaction, and resin property, effectively assisting in the initial phase of our combinatorial chemistry efforts. Our results showed that solid-phase organic reactions proceed faster than generally speculated. In addition, we have shown that reactions on the surface and in the interior of the bead occur at the same rate for reactions studied. The reaction on the TentaGel resin was shown to be not faster than reactions on Wang resin, suggesting that the diffusion of the substrate into polystyrene bead copolymerized with 1% divinylbenzene is not rate-limiting. Finally, the capability of obtaining IR spectra from the partial surface of a single bead demonstrated the femtomolar detection limit of single bead FTIR microspectroscopy. 相似文献
992.
Tse-Chiang Chang 《中国化学会会志》1985,32(1):1-4
In the variational optimization of a trial function the proper functional to be varied is the Rayleigh quotient with the normalization constraint explicitly imposed. It will be shown that only under certain very rigorous conditions can one use the energy functional to replace the Rayleigh quotient and that, therefore, the normalization constraint is by no means a matter of no consequence. 相似文献
993.
[Chemical reaction: see text] Polysubstituted furans and highly functionalized 2H-pyrans were prepared in good yields by DABCO-catalyzed reactions of alpha-halo carbonyl compounds with dimethyl acetylenedicarboxylate (DMAD) at room temperature. 相似文献
994.
Hydrothermal reactions of 1, 2, 4‐benzenetricarboxylic acid, 1, 10‐phenanthroline and transition metal cations including ZnII or CoII, in basified aqueous solution gave rise to two complexes, [Zn3(btrc)2(1, 10‐phen)2(H2O)2]n ( 1 ), and [Co3(btrc)2(1, 10‐phen)2(H2O)2]n ( 2 ) (btrc = 1, 2, 4‐benzenetricarboxylate, and 1, 10‐phen = 1, 10‐phenanthroline). 1 2 crystalize isotypically in the triclinic space group P1¯. The btrc ligand acts as multi‐dentate bridging ligand in both compound 1 and 2 to link up transition metal atoms into lamella networks, which are further attached into three‐dimensional frameworks through complex hydrogen bonding and π‐π interactions. The photoluminescence spectrum for compound 1 has also been studied. The corresponding reaction with Cu2+ follows another pathway. 相似文献
995.
The Suzuki cross-coupling methodology provides a facile synthetic approach for the modular preparation of meso-tetraaryl cofacial bisporphyrins anchored by xanthene and dibenzofuran. This synthetic method furnishes cofacial bisporphyrin templates with enhanced steric and electronic protection from mu-oxo formation and oxidative degradation. The ability of these platforms to support multielectron oxidation chemistry mediated by proton-coupled electron transfer (PCET) is demonstrated by their reactivity for the catalytic disproportionation of hydrogen peroxide to oxygen and water. 相似文献
996.
997.
K. Chang Song 《Journal of Sol-Gel Science and Technology》1998,13(1-3):1017-1021
Mullite fibers were synthesized from an aqueous solution of aluminum isopropoxide, aluminum nitrate and tetraethylorthosilicate by the Sol-Gel method. The starting solution was prepared by adding aluminum isopropoxide and tetraethylorthosilicate simultaneously to an aluminum nitrate aqueous solution. The spinnability of the starting solution was investigated by varying the molar ratio of aluminum isopropoxide/aluminum nitrate in the solution. Gel fibers were obtained from solutions in a composition range of aluminum isopropoxide/aluminum nitrate of 3 to 5. Gels obtained from spinnable solutions appeared to have high homogeneity in the mixing of the Al/Si components, leading to a sharp 980°C exothermic peak in the DTA curve and a mullitization temperature of 1000°C. However, in the case of gels obtained from unspinnable solutions, a small 980°C exothermic peak was detected, and the mullitization temperature was as high as 1200°C, probably due to greater heterogeneity in the mixing of the Al/Si components. 相似文献
998.
Taxumairols X--Z,new taxoids from Taiwanese Taxus mairei 总被引:1,自引:0,他引:1
In addition to 19-dydroxybaccatin III, 1beta-hydroxy-5 alpha-deacetylbaccatin I, taxayuntin G and 13-O-deacetyltaxumairol Z (4), three new taxane diterpenoids, taxumairols X (1), Y (2), Z (3) have been isolated from extracts of the Formosan Taxus mairei (LEMEE & LEVL.) S. Y. HU. Compounds 1-2 belong to the 11(15-->1)-abeo-taxane system, having a tetrahydrofuran ring at C-2, C-3, C-4 and C-20. The new compound 3 and 4, which was misidentified previously are derivatives of 11(15-->1)-abeo-taxane with an intact oxirane system. The structures of compounds 1-4 were elucidated on the basis of extensive two dimensional (2D)-NMR analysis. 相似文献
999.
Jian Kang Chang Hong Huo Zhe Li Zuo Ping Li Department of Natural Medicine Chemistry Hebei Medical University Shijiazhuang China 《中国化学快报》2007,(2)
A new ceramide and its glycoside were isolated from the flower of Albizia julibrissin. Their structures were established as (25,35,4R,8E)-2-[(2'R)-hydroxyhexadecanoylamino]-8-tetra-cosene-l,3,4-triol(I)and 1-O-β-D-glucopyranosy1-(2S,3S,4R,8E)-2-[(2'R)-hydroxy-hexade-canoylamino]-8-tetracosene-1,3,4-triol (II) on the basis of chemical and spectroscopic studies. 相似文献
1000.
New mesoporous niobium oxides with 5, 10, and 15 mol% vanadium(V) doped into the walls of the structure were synthesized by the ligand-assisted templating method with an octadecylamine template. These materials were characterized by XRD, XPS, EPR, elemental analysis, and nitrogen adsorption before being treated with excess bis(benzene)chromium to give new composites with an organometallic phase in the walls. All materials were also characterized by EPR, XRD, nitrogen adsorption, XPS, SQUID magnetometry, and elemental analysis. The materials with higher percentages of vanadium absorbed more bis(benzene)chromium, because this process depends largely on the electron transfer between the organometallic and the walls of the mesostructure and vanadium(V) is a stronger oxidant than niobium(V). Conductivity studies on these materials revealed that the ratio of Cr(0) to Cr(l) in the pores was more important than the absolute Cr loading level in governing electron transport properties but that increasing the V content led to more insulating behavior regardless of the Cr concentration. Solid-state 2H NMR studies on perdeuteriobenzene analogues of these composites showed the presence of the neutral and cationic Cr species in different ratios depending on the loading. Tumbling of these species was also slow on the NMR time scale, indicating that the charge-carrying Cr species are not rapidly moving through the pore channels of the mesostructure. This suggests that the walls of the structure may play a key role in charge transfer in these composites, contrary to what was previously believed. 相似文献