全文获取类型
收费全文 | 136377篇 |
免费 | 1888篇 |
国内免费 | 542篇 |
专业分类
化学 | 60729篇 |
晶体学 | 1130篇 |
力学 | 7614篇 |
综合类 | 5篇 |
数学 | 41919篇 |
物理学 | 27410篇 |
出版年
2023年 | 403篇 |
2022年 | 612篇 |
2021年 | 847篇 |
2020年 | 901篇 |
2019年 | 923篇 |
2018年 | 11136篇 |
2017年 | 10911篇 |
2016年 | 7866篇 |
2015年 | 2487篇 |
2014年 | 2033篇 |
2013年 | 4084篇 |
2012年 | 7248篇 |
2011年 | 13703篇 |
2010年 | 7828篇 |
2009年 | 7952篇 |
2008年 | 9551篇 |
2007年 | 11448篇 |
2006年 | 2977篇 |
2005年 | 3921篇 |
2004年 | 3724篇 |
2003年 | 3838篇 |
2002年 | 2656篇 |
2001年 | 1526篇 |
2000年 | 1516篇 |
1999年 | 1047篇 |
1998年 | 888篇 |
1997年 | 790篇 |
1996年 | 1009篇 |
1995年 | 700篇 |
1994年 | 736篇 |
1993年 | 709篇 |
1992年 | 675篇 |
1991年 | 591篇 |
1990年 | 616篇 |
1989年 | 525篇 |
1988年 | 517篇 |
1987年 | 496篇 |
1986年 | 471篇 |
1985年 | 594篇 |
1984年 | 572篇 |
1983年 | 441篇 |
1982年 | 448篇 |
1981年 | 452篇 |
1980年 | 412篇 |
1979年 | 380篇 |
1978年 | 349篇 |
1977年 | 333篇 |
1976年 | 341篇 |
1974年 | 297篇 |
1973年 | 329篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The method of capillary isotachophoresis with conductivity detection was applied for the determination of the physico-chemical characteristics (conditional stability constants log beta') of holmium and yttrium complexes with DTPA (diethylenetriaminepentaacetic acid) and DOTA (1,4,7,10-tetraazadodecane-N,N',N',N'-tetraacetic acid). The log beta' determination is based on the linear relation between the stability constants of lanthanide-DTPA (lanthanide-DOTA) complexes and the reduction of the zone of the complex owing to the bleeding phenomena (liberating free metal ion). The stability constants calculated using this relationship are comparable with the literary data obtained by other methods for both holmium (log beta'(Ho-DTPA)=21.9, log beta'(Ho-DOTA)=24.5) and yttrium complexes (log beta'(Y-DTPA)=21.2, log beta'(Y-DOTA)=24.4). Capillary isotachophoresis was applied for the determination of the optimum composition of the reaction mixture (metal:ligand ratio) as well. 相似文献
992.
Conejo-García A Campos JM Entrena A Sánchez-Martín RM Gallo MA Espinosa A 《The Journal of organic chemistry》2003,68(22):8697-8699
A complete study of the conformational behavior of 4,8-diaza-3(1,4),9(4,1)-dipyridina-1,6(1,4)-dibenzenacyclodecaphan-3(1),9(1)-bis(ilium) bishexafluorophosphate is described. This study allows us to conclude that the process observed by which the different chemical shifts of the pyridinium protons show coalescence at a high-temperature 1H NMR is the rotation around the C-N bond, whereas the conformational equilibrium between the four conformers is produced at low temperature. 相似文献
993.
ágnes Zsigmond Ramóna Madácsi Ferenc Notheisz Erzsébet Mernyák and Ferenc Joó 《Reaction Kinetics and Catalysis Letters》2006,87(2):297-304
Summary [RuCl2(PPh3)3], [{RuCl2(TPPMS)2}2] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids.
In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case
of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared
traditionally in a more complicated way. 相似文献
994.
Fernández G del Mar Graciani M Rodríguez A Múñoz M Moyá ML 《Journal of colloid and interface science》2000,225(1):47-53
The ligand substitution reactions Fe(CN)(5)(4-(t)bupy)(3-) + 4-CNpy and Fe(CN)(5)(4-(t)bupy)(3-) + pzCO(2)(-) (4-(t)Bupy = 4-tert-butylpyridine; 4-CNpy = 4-cyanopyridine; pzCO(2)(-) = pyrazinecarboxylate) were studied in several aqueous salt and micellar solutions. Kinetic data in aqueous solutions showed that the two processes follow a dissociative mechanism, D, and the dependence of the first-order rate constants on [salt] on electrolyte aqueous solutions allow the estimation of the activation volumes corresponding to both reactions. Under true first-order conditions no kinetic micellar effects were found in anionic (SDS) and nonionic (Triton X-100) aqueous micellar solutions. In cationic micellar solutions (CTAB, CTAC, and TTAB) small kinetic micellar effects were found. These were related to the different ionic concentrations and the different polarity and structure of the Stern layer surrounding the cationic micellar aggregates, where the reactions take place, with respect to pure water. Copyright 2000 Academic Press. 相似文献
995.
L. C. Balbás J. A. Alonso G. Borstel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1987,6(3):219-226
The non local weighted-density approximation (WDA) to the exchange-correlation potentialV xc (r) is used to compute electron densities, ionization potentials and electron affinities of several atoms and ions. Especial care is taken in calculating and discussing 〈r 2〉 in noble gas atoms. Good results are obtained for all those quantities, but it is critical that the WDA is applied in such a way that it preserves the correct larger behaviour ofV xc (r). A comparison of the calculated electron density with that of the Hartree-Fock method shows the effects of coulomb correlation. The density rearrangements upon the introduction of correlation agree qualitatively with the results of Configuration-Interaction calculations 相似文献
996.
The photometric and fluorometric characteristics of the complex formed by 1,4-dihydroxyanthraquinone with Y(III) in 20–80% water-ethanol solution are described by the study of several variables. The stoichiometry and stability constant of the complex in the solution are 1:1 and log K = 4.57, respectively. The 1,4-dihydroxyanthraquinone-Y(III) solid complex has been prepared and studied by infrared spectroscopy and thermal analysis. The thermal behavior of this compound has been studied using thermogravimetry and differential scanning calorimetry techniques and the residue verified by X-ray diffraction. 相似文献
997.
The crystal structure of 1-[N-(2-aminoethyl)aminopropyl]silatrane has been determined by x-ray diffraction at room temperature. The Si←N bond distance (2.165(2) Å) is in the range observed for other 1-X-propylsilatranes (X = CN, OH, SH, Cl and SCN). The structure is partially disordered: the silatrane moiety displays a disorder that is typical for silatranes and the aminoethyl group terminating the planar chain linked to silicon is rotationally disordered. 相似文献
998.
A. Dávid G. Horváth Z. Mészáros T. Meisel Z. Halmos 《Journal of Thermal Analysis and Calorimetry》1974,6(1-2):59-66
The thermal behaviour of tetrahydroperparine (THP) and its derivatives with various acids has been investigated. The acid is liberated from the formate derivative basically in two steps, while the other aliphatic acids are released quantitatively before the thermal decomposition of the THP molecule. The thermoanalytical curves, electrical conductivity data measured in the molten phase, and infrared spectra prove that while part of the formic acid is hydrogen-bonded the other part is bound ionically in the molecule. It may be assumed that the marked biological activity of the compound can be explained by this difference in the nature of the bonds. 相似文献
999.
Santi Tungprapa Tanarinthorn Puangparn Monchawan Weerasombut Ittipol Jangchud Porntiva Fakum Somsak Semongkhol Chidchanok Meechaisue Pitt Supaphol 《Cellulose (London, England)》2007,14(6):563-575
This paper reports an investigation of the effects of solvent system, solution concentration, and applied electrostatic field
strength (EFS) on the morphological appearance and/or size of as-spun cellulose acetate (CA) products. The single-solvent
systems were acetone, chloroform, N,N
-dimethylformamide (DMF), dichloromethane (DCM), methanol (MeOH), formic acid, and pyridine. The mixed-solvent systems were
acetone–DMAc, chloroform–MeOH, and DCM–MeOH. Chloroform, DMF, DCM, MeOH, formic acid, and pyridine were able to dissolve CA,
forming clear solutions (at 5% w/v), but electrospinning of these solutions produced mainly discrete beads. In contrast, electrospinning of the solution of
CA in acetone produced short and beaded fibers. At the same solution concentration of 5% (w/v) electrospinning of the CA solutions was improved by addition of MeOH to either chloroform or DCM. For all the solvent systems
investigated smooth fibers were obtained from 16% (w/v) CA solutions in 1:1, 2:1, and 3:1 (v/v) acetone–DMAc, 14–20% (w/v) CA solutions in 2:1 (v/v) acetone–DMAc, and 8–12% (w/v) CA solutions in 4:1 (v/v) DCM–MeOH. For the as-spun fibers from CA solutions in acetone–DMAc the average diameter ranged between 0.14 and 0.37 μm
whereas for the fibers from solutions in DCM–MeOH it ranged between 0.48 and 1.58 μm. After submersion in distilled water
for 24 h the as-spun CA fibers swelled appreciably (i.e. from 620 to 1110%) but the physical integrity of the fibrous structure
remained intact. 相似文献
1000.
T. Datta Samanta S. Laskar D. Nayak S. Lahiri 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(2):323-325
Binding ability of mercury, thallium, lead and bismuth with Erythrina variegata seed protein have been investigated using tracer packet technique. Due to the lack of standard methods, inter-comparisons
have been made among three different approaches, like trichloroacetic acid (TCA) precipitation, isoelectric precipitation
and dialysis of protein after incubation with the metals. Good agreement was observed for all the cases except that of lead. 相似文献