全文获取类型
收费全文 | 44909篇 |
免费 | 1477篇 |
国内免费 | 213篇 |
专业分类
化学 | 29356篇 |
晶体学 | 329篇 |
力学 | 800篇 |
综合类 | 4篇 |
数学 | 7981篇 |
物理学 | 8129篇 |
出版年
2023年 | 281篇 |
2022年 | 577篇 |
2021年 | 764篇 |
2020年 | 703篇 |
2019年 | 777篇 |
2018年 | 831篇 |
2017年 | 754篇 |
2016年 | 1558篇 |
2015年 | 1241篇 |
2014年 | 1345篇 |
2013年 | 2656篇 |
2012年 | 2773篇 |
2011年 | 3005篇 |
2010年 | 1907篇 |
2009年 | 1777篇 |
2008年 | 2641篇 |
2007年 | 2564篇 |
2006年 | 2354篇 |
2005年 | 2193篇 |
2004年 | 1863篇 |
2003年 | 1478篇 |
2002年 | 1271篇 |
2001年 | 934篇 |
2000年 | 814篇 |
1999年 | 654篇 |
1998年 | 497篇 |
1997年 | 489篇 |
1996年 | 607篇 |
1995年 | 448篇 |
1994年 | 461篇 |
1993年 | 421篇 |
1992年 | 390篇 |
1991年 | 374篇 |
1990年 | 331篇 |
1989年 | 283篇 |
1988年 | 266篇 |
1987年 | 260篇 |
1986年 | 264篇 |
1985年 | 344篇 |
1984年 | 354篇 |
1983年 | 235篇 |
1982年 | 267篇 |
1981年 | 249篇 |
1980年 | 236篇 |
1979年 | 169篇 |
1978年 | 168篇 |
1977年 | 172篇 |
1976年 | 149篇 |
1975年 | 132篇 |
1973年 | 133篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Casas JS Castaño MV García-Tasende MS Rodríguez-Castellón E Sánchez A Sanjuán LM Sordo J 《Dalton transactions (Cambridge, England : 2003)》2004,(13):2019-2026
Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature. 相似文献
992.
The molecular structure and properties of 7-azaindole in its first four singlet states were studied with a view to improving current understanding of the photophysical behavior of its C(2h) dimer. This dimer, which exhibits a double proton transfer via its two hydrogen bonds upon electronic excitation, has for 35 years been used as a model for the photophysical behavior of DNA base pairs. Electronic excitation of 7-azaindole simultaneously increases its acidity and basicity; these changes facilitate a concerted mechanism for the double proton transfer in the dimer. In this work, we found the acidity and basicity changes to occur only in its first pi,pi(*) excited singlet state. 相似文献
993.
Different transformations of chiral epoxy esters 1 afford two different amino gamma-butyrolactones 2 and 6, and amino gamma-butenolides 8, by different nucleophilic opening-closing processes. [reaction: see text] 相似文献
994.
The three-body classical trajectory Monte-Carlo (CTMC) method is used to investigate positron-argon atom collisions. The total ionization cross sections are presented along with singly and doubly differential cross sections. The existence of the cusp-like peak in the triply differential electron and positron spectra at positron impact is predicted. 相似文献
995.
Shilov VN Delgado AV González-Caballero F Horno J López-García JJ Grosse C 《Journal of colloid and interface science》2000,232(1):141-148
Electrophoresis is one of the electrokinetic phenomena most widely investigated, both from a fundamental point of view and as a research tool in academia and industry. However, the dependence between electrophoretic mobility and zeta potential is, in a general case, far from simple, because of the many physical processes involved. In this work, we first describe qualitatively and (in some cases) quantitatively the time behavior of the dipole moment induced in the electrical double layer by an applied electric field. Further, a simple relationship is deduced between the dipole moment and the electrophoretic mobility. Through the analysis of the time dependence of the former, it is possible to resolve the different contributions to the stationary values of the mobility. Three characteristic relaxation times are distinguished in the time evolution of the dipole moment: tau(H) (the time needed for hydrodynamic flows to be established), tau(MW) (time for ionic electromigration to develop), and tau(VD) (after this time, diffusion flows are established in the system, and the double layer polarization is complete). This means that different mechanisms are operating on the double layer for different times after the application of the field, and that computing the mobility at such different times is equivalent to calculating the steady-state electrophoretic mobility under different approximations. A comparison is shown between estimated and computed mobility values as functions of time and of zeta potential, confirming the validity of the asymptotic calculations. Copyright 2000 Academic Press. 相似文献
996.
Inspired by the determination of the structure of the nitrogenase enzyme cofactor by Rees et al., the binding of an N2 molecule to some model iron-sulfur compounds was investigated usingab initio calculations. Side-on and end-on coordination to one two and four iron centers were investigated. In most cases, the N2 is loosely bound and retains its internal triple bond, but a few examples are found where the N2 is “activated” and has a longer N-N bond length. 相似文献
997.
S. Szabó 《Journal of Electroanalytical Chemistry》1977,77(2):193-203
Investigations have shown that copper and silver ions deposited at more positive potentials than the Nernst potential—similarly to bismuth ions—are not adsorbed but form alloys with palladium. Similarly, in the case of metal deposition via the ionization of sorbed hydrogen, the same alloys were formed as observed by the potentiostatic method. 相似文献
998.
Sánchez-Moreno MJ Gómez-Coca RB Fernández-Botello A Ochocki J Kotynski A Griesser R Sigel H 《Organic & biomolecular chemistry》2003,1(10):1819-1826
The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided. 相似文献
999.
Eles J Kalaus G Greiner I Kajtár-Peredy M Szabó P Keserû GM Szabó L Szántay C 《The Journal of organic chemistry》2002,67(21):7255-7260
The first syntheses of the alkaloids (-)-mehranine (3), (+)-voaphylline/conoflorine (4), (+)-N(a)-methylvoaphylline/hecubine (5), and (-)-lochnericine (2) were achieved by stereoselective epoxidation starting from (-)-tabersonine (1), through intermediates with the aspidospermane and quebrachamine skeleton. 相似文献
1000.
Antibacterial activity of methylated chitosan and chitooligomer derivatives: Synthesis and structure activity relationships 总被引:1,自引:0,他引:1
Ögmundur Vidar Rúnarsson Tapio Nevalainen Tomi Järvinen Jón M. Einarsson Margrét Valdimarsdóttir 《European Polymer Journal》2007,43(6):2660-2671
The purpose of this study was to synthesize series of methylated chitosaccharide derivatives, possessing various degree of methylation, and to determine their structure activity relationship (SAR) with regard to their antibacterial effect against Staphylococcus aureus. Chitosan polymer and chitooligomers were used as starting materials and were methylated by reaction with methyl iodide. Depending on the reaction conditions the degree of N-quaternization ranged from 0% to 74%, with varying degree of N,N-dimethylation, N-monomethylation and O-methylation. More selective N-quaternization could be obtained with protection group strategy. At pH 5.5 the chitosaccharide polymers and their methylated derivatives were active against S. aureus with minimal inhibitory concentration (MIC) ranging from 16 to 512 μg/mL. At pH 7.2 the non-quaternized derivatives were inactive but their highly N-quaternized derivatives showed MIC as low as 8 μg/mL. The chitooligomers, as well as their derivatives, were inactive at both pH’s. The SAR studies revealed that N-quaternization was mainly responsible for the antibacterial effects at pH 7.2, whereas it did not contribute to the antibacterial activity under acidic conditions. 相似文献