全文获取类型
收费全文 | 76603篇 |
免费 | 14719篇 |
国内免费 | 7102篇 |
专业分类
化学 | 68510篇 |
晶体学 | 1052篇 |
力学 | 2918篇 |
综合类 | 538篇 |
数学 | 6550篇 |
物理学 | 18856篇 |
出版年
2024年 | 121篇 |
2023年 | 803篇 |
2022年 | 1336篇 |
2021年 | 1588篇 |
2020年 | 2747篇 |
2019年 | 3951篇 |
2018年 | 2274篇 |
2017年 | 1969篇 |
2016年 | 5059篇 |
2015年 | 5207篇 |
2014年 | 5511篇 |
2013年 | 6787篇 |
2012年 | 6564篇 |
2011年 | 5763篇 |
2010年 | 5476篇 |
2009年 | 5412篇 |
2008年 | 5212篇 |
2007年 | 4300篇 |
2006年 | 3946篇 |
2005年 | 3757篇 |
2004年 | 3135篇 |
2003年 | 2669篇 |
2002年 | 3309篇 |
2001年 | 2456篇 |
2000年 | 2249篇 |
1999年 | 1335篇 |
1998年 | 771篇 |
1997年 | 641篇 |
1996年 | 613篇 |
1995年 | 538篇 |
1994年 | 517篇 |
1993年 | 456篇 |
1992年 | 346篇 |
1991年 | 324篇 |
1990年 | 290篇 |
1989年 | 205篇 |
1988年 | 166篇 |
1987年 | 106篇 |
1986年 | 125篇 |
1985年 | 101篇 |
1984年 | 58篇 |
1983年 | 56篇 |
1982年 | 49篇 |
1981年 | 38篇 |
1980年 | 18篇 |
1979年 | 18篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1957年 | 7篇 |
1936年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Yamamoto Y Terui N Tachiiri N Minakawa K Matsuo H Kameda T Hasegawa J Sambongi Y Uchiyama S Kobayashi Y Igarashi Y 《Journal of the American Chemical Society》2002,124(39):11574-11575
Paramagnetic NMR and optical studies of the oxidized forms of mesophile Pseudomonas aeruginosa cytochrome c(551) and its quintuple mutant (F7A/V13M/F34Y/E43Y/V78I), and thermophile Hydrogenobacter thermophilus cytochrome c(552) demonstrated that the amino acid side chain packings in the protein interior influence the coordination bond between the heme iron and the axial methionine in the proteins. The strength of heme axial coordinations was found to correlate with the overall protein thermostability. 相似文献
992.
Yi‐Jun Huang Guo‐Rong Qi Yu‐Hua Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1142-1150
A double metal‐cyanide catalyst based on Zn3[Co(CN)6]2 was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. 13C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002 相似文献
993.
N. S. Mosyagin A. V. Titov R. J. Buenker H.‐P. Liebermann A. B. Alekseyev 《International journal of quantum chemistry》2002,88(5):681-686
Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
994.
The reactions of transition metal salts with taurine 5‐chlorosalicylaldelyde Schiff base gave two complexes [Ni(TCSSB)(H2O)3].H2O (1) and [Cu(TCSSB)(H2O)2]2[Cu(TCSSB)2].6H2O (2) (TCSSB=taurine‐5‐chlorosalicylaldelyde Schiff base), which were characterized by elemental analysis and X‐ray diffraction analysis. The complex 1 crystallized in monoclinic system with space group P2 1/c, and a=1.4816(2) nm, b=1.3953(2) nm, c= 0.7466(1) nm, β= 100.499(3)°, V=1.5176(4) nm3, Z=4, and an infinite 3‐D network structure was formed by hydrogen bonds among sulfo group, crystal water and coordinated water. Complex 2 crystallized in triclinic system with space group P1 , with the cell parameters: a = 0.6413(2) nm, b= 1.4596(3) nm, c= 1.6188(4) nm, a= 102.473(5)°, β= 98.979(4)°, γ=101.739°, V=1.4165(6) nm3, Z=1. The coordination environment between Cu(1) and Cu(2) is different. Cu(1) is slightly distorted square pyramidal while Cu(2) is distorted square‐plane. The complex 1 is mononuclear while the complex 2 is made up of two coordinated subunits, namely [Cu(TCSSB)2] and [CU(TCSSB)(H2O)2]2. Besides that the TG‐DTG of the complex 1 was analyzed, the thermal decomposition reaction of the complex was studied under a non‐isothermal condition by TG‐DTG. The TG and DTG curves indicate that the complex was decomposed in three stages: . 相似文献
995.
An electronic protein transfer technique is described for achieving the rapid and efficient recovery of sodium dodecyl sulfate (SDS)-protein complexes from polyacrylamide gels. This process involves the use of small-dimension capillaries in physical contact with a resolved protein band within the polyacrylamide gel, providing a large potential drop and high electric field strength at the capillary/gel interface. Several factors controlling the electronic protein transfer, including the applied electric field strength, the electrophoresis buffer concentration, and the capillary dimension, are studied to further enhance the use of field-amplification for sample stacking of extracted SDS-protein complexes. As a result of sample stacking, the extracted proteins from a 50 ng gel loading are present in a narrow ( approximately 80 nL) and highly concentrated (0.46 mg/mL or 3.3 x 10(-5) M for cytochrome c) solution plug. Three model proteins with molecular mass ranging from 14 kDa (cytochrome c) to 116 kDa (beta-galactosidase) are stained by Coomassie blue and electrophoretically extracted from gels with protein loadings as low as 50 ng. The capillary format of the electronic protein transfer technique allows direct deposition of extracted proteins onto a matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) target. Various matrices and solvent compositions are evaluated for the analysis of extracted and concentrated SDS-protein complexes using MALDI-MS. The electronic protein transfer technique, when operated under optimized conditions, is demonstrated for the effective (>70% recovery), speedy (less than 5 min), and sensitive MS identification of gel resolved proteins (as low as 50 ng). 相似文献
996.
Qi‐Wei Zhang Yi‐Hang Wen Yun‐Long Feng 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m255-m257
The title compound, [Zn2(C5H6O4)2(C13H14N2)]n or [Zn2(glu)2(bpp)]n, is a novel zinc polymer based on mixed flexible glutarate (glu) and 1,3‐di‐4‐pyridylpropane (bpp) ligands. The ZnII center has a distorted tetrahedral geometry and the central atom of the bpp ligand is located at a special site with a C2 axis passing through it. A layer is formed by Zn–glu bonding. Such layers are pillared by bpp ligands, forming a three‐dimensional framework with large channels. The inverted interpenetration of two three‐dimensional frameworks completes the molecular structure. 相似文献
997.
Application of L-Cysteine-Capped ZnS Nanoparticles in the Determination of Nucleic Acids Using the Resonance Light Scattering Method 总被引:2,自引:0,他引:2
Yongxin?LiEmail author Jinlong?Chen Shujuan?Zhuo Yuqin?Wu Changqin?Zhu Lun?Wang 《Mikrochimica acta》2004,146(1):13-19
Nanometer-sized L-cysteine-capped ZnS particles were synthesized by a colloidal aqueous method. The functionalized nanoparticles are water-soluble and suitable for biological applications. In Tris-HCl buffer solution, nucleic acids combine with cysteine-capped nano-ZnS particles by intermolecular forces to form larger nanoparticles. There are two resonance light scattering peaks at 304.5nm and 373.8nm, respectively. The enhanced RLS is related to the concentration of nucleic acids in the range of 0.04 to 1.2µgmL–1 for calf thymus DNA and 0.2 to 1.0µgmL–1 for fish sperm DNA. The detection limits (3) are 19ngmL–1 for calf thymus DNA and 23ngmL–1 for fish sperm DNA, respectively. Four synthetic samples were analyzed satisfactorily. 相似文献
998.
Four new 28‐noroleanane‐derived spirocyclic triterpenoids, compounds 1 – 4 , were isolated from the rhizomes of Phlomis umbrosa. Their structures were elucidated on the basis of 1D‐ and 2D‐NMR analyses, in combination with high‐resolution MS experiments. 相似文献
999.
Hayati Türkmen Resul Sevinek Bekir etinkaya Santiago García‐Granda Muhittin Aygün 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(6):m277-m279
The title complex, [PdCl2(C21H26N2)(C18H15P)], shows slightly distorted square‐planar coordination around the PdII metal centre. The Pd—C bond distance between the N‐heterocyclic ligand and the metal atom is 2.028 (5) Å. The dihedral angle between the two trimethylphenyl ring planes is 36.9 (2)°. 相似文献
1000.
Zhaoyang Cheng Shipei Xing Jun Guo Biao Cheng Lan‐Fang Hu Xing‐Hong Zhang Zhan Lu 《中国化学》2019,37(5):457-461
A regioselective double 1,1‐hydrosilylation of terminal aliphatic alkynes with primary silanes catalyzed by one cobalt catalyst has been developed. gem‐Bis(dihydrosilyl)alkanes containing four silicon‐hydrogen bonds are efficiently constructed in an atom‐economical manner. Tolerated substrates include simplest alkyne‐ethyne, a complicated drug derivative and various functionalized terminal aliphatic alkynes. Asymmetric approach using two catalysts is achieved with excellent enantioselectivities to access corresponding chiral products. The transformations of Si—H bonds into Si—C, Si—O, and Si—F bonds and the synthesis of enantioriched α‐hydroxysilane show synthetic utility. 相似文献