全文获取类型
收费全文 | 4344篇 |
免费 | 124篇 |
国内免费 | 20篇 |
专业分类
化学 | 2812篇 |
晶体学 | 39篇 |
力学 | 82篇 |
数学 | 843篇 |
物理学 | 712篇 |
出版年
2023年 | 42篇 |
2022年 | 95篇 |
2021年 | 125篇 |
2020年 | 98篇 |
2019年 | 122篇 |
2018年 | 132篇 |
2017年 | 111篇 |
2016年 | 151篇 |
2015年 | 121篇 |
2014年 | 125篇 |
2013年 | 271篇 |
2012年 | 236篇 |
2011年 | 302篇 |
2010年 | 192篇 |
2009年 | 194篇 |
2008年 | 241篇 |
2007年 | 227篇 |
2006年 | 223篇 |
2005年 | 210篇 |
2004年 | 174篇 |
2003年 | 137篇 |
2002年 | 113篇 |
2001年 | 72篇 |
2000年 | 53篇 |
1999年 | 38篇 |
1998年 | 38篇 |
1997年 | 33篇 |
1996年 | 26篇 |
1995年 | 22篇 |
1994年 | 25篇 |
1993年 | 32篇 |
1992年 | 18篇 |
1991年 | 31篇 |
1990年 | 17篇 |
1989年 | 14篇 |
1987年 | 15篇 |
1986年 | 20篇 |
1985年 | 22篇 |
1984年 | 30篇 |
1983年 | 20篇 |
1982年 | 20篇 |
1981年 | 27篇 |
1980年 | 22篇 |
1979年 | 25篇 |
1978年 | 26篇 |
1977年 | 27篇 |
1975年 | 20篇 |
1974年 | 15篇 |
1958年 | 13篇 |
1955年 | 15篇 |
排序方式: 共有4488条查询结果,搜索用时 0 毫秒
111.
Based on a computer-assisted analysis of the three-dimensional structure of the binary complex of E.coli dihydrofolate reductase (DHFR) with methotrexate, 5-(N-arylnortropan-3-yl)- and 5-(N-arylpiperidin-4-yl)-2,4-diaminopyrimidines 2 and 4 were designed as inhibitors of DHFR. Syntheses of the designed compounds have been carried out. The most potent compound 2a inhibited E. coli DHFR with Ki = 0.49.10?9M. The activities within the series of compounds synthesized could be rationalized by molecular-modelling experiments which served as the basis of this work. Several compounds within the presented series exhibit antimalarial activities in vitro and in vivo. 相似文献
112.
Plamen A. Demirev Alexander S. Dyulgerov Ivan P. Bangov 《Journal of mathematical chemistry》1991,8(1):367-382
A new type of topological index is proposed. Its definition is based on the concept of atomic charge distributions in organic molecules. Introduction of electronic in addition to purely topologic factors allows consideration of heteroatom-containing structures as well. It is demonstrated that the index has a low degree of degeneracy, thus suggesting it can be used for coding chemical structures, discrimination of redundancies in structure generation programs, and studies of quantitative structure-activity relationships for heteroatom-containing structures. 相似文献
113.
Summary The new concept of the resonance energy in conjugated hydrocarbons introduced by Jiang Y, Zhang H (1989) Theor Chim Acta 75:279 is further developed. This model is based on expansion of the -electron energy in terms of moments which are also equal to numbers of closed walks in a molecular graph. The reference system is established by counting only acyclic walks, i.e. those tracing only on acyclic subgraphs. Because acyclic walks could be counted only up to some finite length, the energy of the reference system has been evaluated by truncating higher terms in the expansion. In this paper a finite expression for the energy of the same reference system is derived, thus allowing its exact evaluation. The exact values differ significantly from the truncated ones. This difference, as well as the discrepancy between exact results and chemical experience, are discussed. 相似文献
114.
We determine explicitly all geometrical operators transforming a linear connection on a vector bundle :EM and a classical linear connection on the base manifoldM into a classical linear connection on the total spaceE. 相似文献
115.
Labuda J Bucková M Heilerová L Silhár S Stepánek I 《Analytical and bioanalytical chemistry》2003,376(2):168-173
Quercetin and rutin as well as catechin and epigallocatechin gallate were investigated, as widely distributed representatives of flavonols and flavanols, respectively, regarding their anti/pro-oxidant properties. The flavonoids are irreversibly oxidized at a dsDNA-modified screen-printed electrode within 0.368 to 0.449 V vs. SHE without binding to DNA. Using the DNA biosensor the detection scheme of a DNA prevention/degradation exploits the [Co(phen)(3)](3+) complex as an electrochemical DNA marker. Antioxidant activity of flavonoids was tested in a model cleavage mixture composed of 5 x 10(-7) mol L(-1) [Cu(phen)(2)](2+) as the catalyst, 1 x 10(-3) mol L(-1) ascorbic acid as the chemical reductant and atmospheric oxygen as the natural oxidant where reactive oxygen radicals are generated. The antioxidant activity increases with the concentration of flavonoids reaching a maximum where pro-oxidative behaviour becomes of importance. The pro-oxidant potency of flavonoids depends on the presence of atmospheric oxygen and follows the order quercetin>rutin>epigallocatechin gallate>catechin. 相似文献
116.
Summary On small columns filled with the inorganic cation-exchanger zirconium phosphate, Zn2+-Cd2+ were quantitatively and Ni2+-Co2+ partly separated. The exchanger was in the NH4+ form, and 0.5–4N NH4Cl served as eluent. With the exchanger in the H+ form, U02
2+ was separated from bivalent cations and ferric iron by stepwise elution with 0.1, 0.5 and 4N HCl solutions.
Zusammenfassung An kleinen Säulen des anorganischen Kationenaustauschers Zirkoniumphosphat wurden Zn2+ und Cd2+ quantitativ, Ni2+ und Co2+ teilweise getrennt. Der Austauscher lag in der NH4+-Form vor, 0,5-bis 4-n Ammoniumchlorid diente als Eluent. Mit der H+-Form des Austauschers wurde UO2 2+ von zweiwertigen Kationen und von Fe3+ durch schrittweise Elution mit 0,1-, 0,5- und 4-n Salzsäure getrennt.
Résumé On a séparé Zn2+-Cd2+ quantitativement et Ni2+-Co2+ partiellement sur de petites colonnes remplies de phosphate de zirconium comme échangeur minéral cationique. L'échangeur se trouvait sous forme NH4+ et l'on a pris NH4Cl 0,5-4N comme éluant. Avec l'échangeur sous forme H+, on a séparé UO2 2+ des cations bivalents et de l'ion ferrique par élution graduelle avec des solutions chlorhydriques 0,1, 0,5 et 4N.相似文献
117.
DNA interchain cross-links formed by acrolein and crotonaldehyde 总被引:1,自引:0,他引:1
Kozekov ID Nechev LV Moseley MS Harris CM Rizzo CJ Stone MP Harris TM 《Journal of the American Chemical Society》2003,125(1):50-61
Acrolein and higher alpha,beta-unsaturated aldehydes are bifunctional genotoxins. The deoxyguanosine adduct of acrolein, 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-hydroxypyrimido[1,2-a]purin-10(3H)-one (8-hydroxy-1,N(2)-propanodeoxyguanosine, 2a), is a major DNA adduct formed by acrolein. The potential for oligodeoxynucleotide duplexes containing 2a to form interchain cross-links was evaluated by HPLC, CZE, MALDI-TOF, and melting phenomena. Interchain cross-links represent one of the most serious types of damage in DNA since they are absolute blocks to replication. In oligodeoxynucleotides containing the sequence 5'-dC-2a, cross-linking occurred in a slow, reversible manner to the extent of approximately 50%. Enzymatic digestion to form 3-(2-deoxy-beta-d-erythro-pentofuranosyl)-5,6,7,8-tetrahydro-8-(N(2)-2'-deoxyguanosinyl)pyrimido[1,2-a]purin-10(3H)one (5a) and reduction with NaCNBH(3) followed by enzymatic digestion to give 1,3-bis(2'-deoxyguanosin-N(2)-yl)propane (6a) established that cross-linking had occurred with the exocyclic amino group of deoxyguanosine. It is concluded that the cross-link is a mixture of imine and carbinolamine structures. With oligodeoxynucleotide duplexes containing the sequence 5'-2a-dC, cross-links were not detected by the techniques enumerated above. In addition, (15)N-(1)H HSQC and HSQC-filtered NOESY spectra carried out with a duplex having (15)N-labeling of the target amino group established unambiguously that a carbinolamine cross-link was not formed. The potential for interchain cross-link formation by the analogous crotonaldehyde adduct (2b) was evaluated in a 5'-dC-2b sequence. Cross-link formation was strongly dependent on the configuration of the methyl group at C6 of 2b. The 6R diastereomer of 2b formed a cross-link to the extent of 38%, whereas the 6S diastereomer cross-linked only 5%. 相似文献
118.
Different inner-sphere coordination environments are observed for the uranyl nitrate complexes formed with octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate in dodecane and in the hydrophobic ionic liquids (ILs) [C(4)mim][PF(6)] and [C(8)mim][N(SO(2)CF(3))(2)]. Qualitative differences in the coordination environment of the extracted uranyl species are implied by changes in peak intensity patterns and locations for uranyl UV-visible spectral bands when the solvent is changed. EXAFS data for uranyl complexes in dodecane solutions is consistent with hexagonal bipyramidal coordination and the existence of UO(2)(NO(3))(2)(CMPO)(2). In contrast, the complexes formed when uranyl is transferred from aqueous nitric acid solutions into the ILs exhibit an average equatorial coordination number of approximately 4.5. Liquid/liquid extraction results for uranyl in both ILs indicate a net stoichiometry of UO(2)(NO(3))(CMPO)(+). The concentration of the IL cation in the aqueous phase increases in proportion to the amount of UO(2)(NO(3))(CMPO)(+) in the IL phase, supporting a predominantly cation exchange mechanism for partitioning in the IL systems. 相似文献
119.
The title compound, [cis-Co(en)2(NO2)2](NO2) (1), crystallizes in the polar, nonenantiomorphic, monoclinic space group, Cc, with lattice constants:a=9.198(2) Å,b=12.444(2),c=9.963(3), and=96.76(2)°;V=1132.39 Å3 andd(calc;Z=4) =1.860 g cm–3. Thus, with NO2– as the counteranion, [cis-Co(en)2(NO2)2] crystallizes in a heterochiral lattice containing racemic pairs of cations. A total of 2699 data were collected over the range of 4°270°; of these, 1859 (independent and withI3(I)) were used in the structural analysis. Data were corrected for absorption (=15.465 cm–1) and the relative transmission coefficients ranged from 0.9934 to 0.7112. Refinement was carried out for both lattice polarities and the finalR(F) andR
w
(F) residuals were, respectively, 0.0242 and 0.0202 for (–––) and 0.0264 and 0.0243 for (+++). Thus, the former was selected as correct for our specimen.Unlike all previous X-ray diffraction studies of the structural properties of the cation [cis-Co(en)2(NO2)2]+, which are found to have a pair of oppositely configured en rings [i.e., () or ()], we find that in1 the cations are in the lowest energy conformation and configuration; i.e., () or (). We attribute this change in configuration to the formation of strong interionic hydrogen bonds between nitrite anion oxygens and the axial—NH2 hydrogens, which markedly weaken the intermolecular and intramolecular hydrogen bonds between ligand—NO2 oxygens and the hydrogens of those same amine moieties. Thus, the nitrite anions behave exactly as nitrate anions, except that the hydrogen bonds found here are stronger than those formed by the latter. This is as expected since the negative charge is delocalized over two, instead of three, oxygens. 相似文献
120.
Stíbr B Holub J Bakardjiev M Pavlík I Tok OL Císarová I Wrackmeyer B Herberhold M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2239-2244
The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed. 相似文献