全文获取类型
收费全文 | 67211篇 |
免费 | 12285篇 |
国内免费 | 5148篇 |
专业分类
化学 | 61829篇 |
晶体学 | 691篇 |
力学 | 2257篇 |
综合类 | 267篇 |
数学 | 5954篇 |
物理学 | 13646篇 |
出版年
2024年 | 90篇 |
2023年 | 585篇 |
2022年 | 976篇 |
2021年 | 1175篇 |
2020年 | 2230篇 |
2019年 | 3507篇 |
2018年 | 1888篇 |
2017年 | 1542篇 |
2016年 | 4519篇 |
2015年 | 4725篇 |
2014年 | 4838篇 |
2013年 | 5992篇 |
2012年 | 5427篇 |
2011年 | 4949篇 |
2010年 | 4693篇 |
2009年 | 4582篇 |
2008年 | 4397篇 |
2007年 | 3622篇 |
2006年 | 3149篇 |
2005年 | 3110篇 |
2004年 | 2592篇 |
2003年 | 2213篇 |
2002年 | 2873篇 |
2001年 | 2120篇 |
2000年 | 1897篇 |
1999年 | 1041篇 |
1998年 | 630篇 |
1997年 | 575篇 |
1996年 | 597篇 |
1995年 | 497篇 |
1994年 | 451篇 |
1993年 | 409篇 |
1992年 | 381篇 |
1991年 | 342篇 |
1990年 | 298篇 |
1989年 | 243篇 |
1988年 | 208篇 |
1987年 | 155篇 |
1986年 | 175篇 |
1985年 | 180篇 |
1984年 | 115篇 |
1983年 | 73篇 |
1982年 | 82篇 |
1981年 | 58篇 |
1980年 | 57篇 |
1979年 | 60篇 |
1978年 | 40篇 |
1976年 | 38篇 |
1974年 | 41篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Yael Diskin‐Posner Goutam Kumar Patra Israel Goldberg 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(6):m344-m346
The title compound, [5,10,15,20‐meso‐tetrakis(4‐hydroxyphenyl)porphyrinato‐κ4N]zinc(II) tris(dibenzo‐24‐crown‐8) methanol tetrasolvate, [Zn(C44H28N4O4)]·3C24H32O8·4CH4O, was synthesized and its molecular structure precisely characterized by low‐temperature single‐crystal analysis. All the components are involved in hydrogen bonding with each other, thus forming an extensively hydrogen‐bonded supramolecular lattice. The functionalized porphyrin moiety coordinates both equatorially and axially to the neighboring species. 相似文献
982.
983.
Synthesis of poly(thiocarbonate)s from the copolymerization of epoxides and carbon disulfide (CS2) remains a tough challenge, due to inevitable oxygen‐sulfur atom scrambling process. In this work, we utilized the oxygen‐sulfur exchange reaction (O‐S ER) to synthesize a random copolymer with monothiocarbonate and trithiocarbonate units from CS2 and phenyl glycidyl ether (PGE) via metal‐free Lewis pairs. The copolymers contained monothiocarbonate and trithiocarbonate units of which the molar fraction could be tuned by varying either the types of Lewis pairs or the reaction temperature. Keeping track on the intermediate provided an insight in the process of O‐S ER and thus gave a hint to control the product structure. Production and consumption of phenyl thioglycidyl ether was the key process to regulate the chain structure. Remarkably, the oxygen atoms of PGE could be excluded out of the chain, resulting in the nearly complete production of poly(trithiocarbonate)s. Correspondingly, the refractive index of this kind of copolymer could be regulated in a wide range of 1.73—1.79 (at 590 nm). 相似文献
984.
A novel type of phosphated puerarin derivatives were synthesized through a simplified Atheron‐Todd reaction for the first time. The structure of these compounds were elucidated by IR, ESI‐MS and NMR. Moreover, the reason the dialkylphophite reagent had different chemselectivities toward different hydroxys on the puerarin was discussed. 相似文献
985.
Mohammed A. Suliman Mohammed A. Gondal Mohamed A. Dastageer Gaik‐Khuan Chuah Chanbasha Basheer 《Photochemistry and photobiology》2019,95(6):1485-1494
An efficient method of photocatalytic degradation of methylparaben in water using Ag nanoparticles (NPs) loaded AgBr‐mesoporous‐WO3 composite photocatalyst (Ag/AgBr@m‐WO3), under visible light is presented. In this process, quantification of methylparaben in water was carried out by high‐performance liquid chromatography (HPLC) and the HPLC results showed a significant reduction of methylparaben in water due to the enhanced of photocatalytic degradation efficiency of Ag/AgBr@m‐WO3. For the material synthesis, highly ordered mesoporous‐WO3 (m‐WO3) was initially synthesized by sol–gel method and AgBr nanoparticles (NPs) were subsequently introduced in the pores of m‐WO3, and finally, the Ag nanoparticles were introduced by light irradiation. The enhanced photocatalytic degradation of methylparaben in water is attributed to the formation of surface plasmonic resonance (SPR) due to the introduction of Ag NPs on the surface of the catalyst. Also, the formation of heterojunction between AgBr and mesoporous‐WO3 in Ag/AgBr@m‐WO3 significantly inhibited the recombination of light‐induced electron‐hole pairs in the semiconductor composite. The morphological and optical characterizations of the synthesized photocatalysts (Ag/AgBr@m‐WO3) were carried out using SEM, TEM, XDR, N2 adsorption–desorption, UV‐VIS diffuse reflectance spectroscopy (DRS). Also, the photocatalytic studies using radical scavengers were carried out and the results indicated that is the main reactive species. 相似文献
986.
We have shown that affinity NMR can be used to edit a NMR spectrum so that ligands that have affinity to DNA can be observed in the presence of other nonbinding molecules. Diffusion encoded spectroscopy (DECODES) can be used to identify the binding ligands. We were able to identify Hoechst 33342 as binding to the Drew-Dickerson dodecamer d(CGCGAATTCGCG)2 in the presence of the nonbinding molecules adenine, adenosine, and thiamine. Affinity NMR appears to be readily applicable to DNA systems for the following reasons. (1) The relaxation rate of the DNA oligonucleotides is favorable, thus the signal intensity loss due to relaxation is not severe. (2) A comparison of the patterns of the DNA cross-peaks upon binding in the two-dimensional total correlation spectroscopy and correlation spectroscopy spectrum are easily performed, and the ligand signals in the two-dimensional DECODES spectrum can be readily identified. (3) The aromatic part of the DNA spectrum is devoid of 2D cross-peaks in these correlation spectra, greatly facilitating the interpretation of the bound ligand in the DECODES spectrum. 相似文献
987.
A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions. 相似文献
988.
Cardiolipin is an important phospholipid present in the mitochondrial inner membrane. It plays a key function in mitochondrial respiration by interacting with many enzymes or cofactors related to oxidative phosphorylation complexes. We have determined the concentration of cardiolipin using on-line 10-N-nonyl acridine orange (NAO) dye interaction capillary electrophoresis (CE) and spectrophotometric detection with a sample throughput of 3 min. In addition to the presence of 0.1 mM NAO, the background electrolyte (BGE) composition has been set at 80% methanol-10% acetonitrile-10% H(2)O (all v/v) to provide both good solubility and the maximum absorbance enhancement at 497 nm for the NAO-cardiolipin complex as compared to NAO alone. Sample consumption for each injection is about 57 nL. A calibration curve is established from 0.5 microM to 0.1 mM with R (2) = 0.9912 with a detection limit of 0.05 microM for cardiolipin. In a blind study, actual mitochondrial cell membrane samples in the microL range before or after UV light exposure were analyzed using the CE method. Cardiolipin concentration decreased in the different parts of the membrane sample upon UV photolysis of the cells. Support for the theory that UV light can induce cardiolipin translocation from the inner membrane (IM) to the outer membrane (OM) was indicated by a significant percentage increase of cardiolipin (as measured by the cardiolipin in the OM as compared to the sum total in the OM and IM) from 30.7 +/- 2.4% before UV light photolysis to 38.3 +/- 2.2% after UV irradiation. 相似文献
989.
Tao He Ying‐Fang Zou Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3367-3378
Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under 60Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under 60Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]0/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002 相似文献
990.
De‐Chun Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(6):o351-o352
In the title compound, N‐(2‐methoxyphenyl)‐4‐nitrobenzylideneamine, C14H12N2O3, the two phenyl rings make a dihedral angle of 48.0 (2)° and the nitro group is at an angle of 6.5 (1)° with respect to its attached phenyl ring. In the crystal structure, molecules are related as centrosymmetric pairs through π–π interactions and are further connected through strong C—H?O hydrogen bonds [C?O 3.4259 (17) Å and C—H?O 167°], forming molecular stacks along [100]. These stacks associate further through longer C—H?O interactions, forming two‐dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described. 相似文献