全文获取类型
收费全文 | 34226篇 |
免费 | 1023篇 |
国内免费 | 443篇 |
专业分类
化学 | 20225篇 |
晶体学 | 187篇 |
力学 | 1756篇 |
综合类 | 18篇 |
数学 | 5640篇 |
物理学 | 7866篇 |
出版年
2022年 | 318篇 |
2021年 | 537篇 |
2020年 | 672篇 |
2019年 | 809篇 |
2018年 | 750篇 |
2017年 | 650篇 |
2016年 | 1088篇 |
2015年 | 808篇 |
2014年 | 962篇 |
2013年 | 1494篇 |
2012年 | 1636篇 |
2011年 | 1844篇 |
2010年 | 1254篇 |
2009年 | 1126篇 |
2008年 | 1471篇 |
2007年 | 1411篇 |
2006年 | 1298篇 |
2005年 | 1172篇 |
2004年 | 995篇 |
2003年 | 900篇 |
2002年 | 927篇 |
2001年 | 692篇 |
2000年 | 501篇 |
1999年 | 440篇 |
1998年 | 392篇 |
1997年 | 392篇 |
1996年 | 390篇 |
1995年 | 352篇 |
1994年 | 303篇 |
1993年 | 337篇 |
1992年 | 323篇 |
1991年 | 321篇 |
1990年 | 329篇 |
1989年 | 300篇 |
1985年 | 341篇 |
1984年 | 339篇 |
1983年 | 292篇 |
1982年 | 331篇 |
1980年 | 300篇 |
1979年 | 340篇 |
1978年 | 373篇 |
1977年 | 361篇 |
1976年 | 451篇 |
1975年 | 386篇 |
1974年 | 422篇 |
1973年 | 425篇 |
1972年 | 381篇 |
1971年 | 344篇 |
1970年 | 330篇 |
1969年 | 307篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
991.
Alexander Apelblat Emanuel Manzurola Zoya Orekhova 《Journal of solution chemistry》2007,36(8):1023-1035
Conductivity measurements of glutaric acid and disodium glutarate in dilute aqueous solutions were performed in the 288.15
to 323.15 K temperature range. The limiting equivalent conductances of glutarate anions, λ
o(HGlut−,T) and λ
o(1/2Glut2−,T), and the dissociation constants of glutaric acid, K
1(T) and K
2(T), were derived by the use of the Onsager and the Quint and Viallard conductivity equations. The applied molecular model was
successfully confirmed by analyzing the conductivities of sodium hydrogen glutarate at 298.15 K. 相似文献
992.
Qian-Feng Zhang Yu-Jie Liu Richard D. Adams Alexander Rothenberger Dieter Fenske Wa-Hung Leung 《Journal of Cluster Science》2006,17(3):445-455
Treatment of tetracopper(I)-phosphonitocavitand [1·Cu4(μ-Cl)4(μ4-Cl)] (2) (1 = tetraphosphonitocavitand [rccc-2,8,14,20-tetrakis-(iso-butyl)-phosphonitocavitand (C44H48O8P4Ph4)]) with PhSeSiMe3 in THF at low temperature afforded a novel polyanionic cluster [pyH]6[(CuCl)9(μ3-SePh)5(μ4-SePh)] (4) as a major product along with a new tetracopper(I)-phosphonitocavitand (3) with a centered μ3-Cl. Molecular structure of anionic cluster in 4 consists of six PhSe− bridging ligands containing five μ3-SePh and one exceptional μ4-SePh bridging nine copper atoms, of which eight copper atoms have trigonal coordination geometry and the other has distorted
tetrahedral geometry.
Dedicated to Professor Han-Qin Liu on the occasion of his 70th birthday. 相似文献
993.
Wei SUN Ya Qin DING Kui JIAO 《中国化学快报》2005,16(11):1515-1518
The interaction of phenosafranine (PSF) with a glycosaminoglycans of heparin (Hep) in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robinson (B-R) buffer solution. The addition of Hep caused decrease of the absorbance of PSF at 532 nm and the redox peak current of PSF. The study showed that an supramolecular complex of PSF-Hep was formed because of the electrostatic attraction of negatively charged Hep with the positively charged PSF, which resulted in the decrease of the equilibrium concentration of PSF in solutions, and the decrease of the absorbance or the peak current of PSF. The stoichiometry of the Hep/PSF complex was further calculated by voltammetric data with the result of 1:1 complex. 相似文献
994.
S. V. Rosokha Ya. D. Lampeka L. N. Zakrevskaya 《Theoretical and Experimental Chemistry》1991,27(1):49-52
A spectrophotometric method has been used to study in sulfuric acid solutions the chelate reduction of nickel(III) compounds NiIIIL, where L are l4-membered tetraazamacrocyclic ligands with a different number of substitutents (from 0 to 0) and double bonds (from U to 4). Based on the comparison of the kinetic characteristics of the redox reactions of the nickel complexes with data on the participation of such compounds in oscillating chemical reactions in the systems NiLBrO–
3-H2SO4 it was concluded that a necessary condition for the creation of OCR in this case is, besides the autocatalytic regime of the oxidation of the [NiL]2+ complex with bromate, the ability of nickel(III) to undergo rapid reduction (k > 10–4 sec–1) by the oxidation of the coordinated macrocyclic ligand.L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of Ukrainian SSR, Kiev. Translated from Teoretichesakaya i ÉksperimentaI'naya Khimiya, Vol. 27, No. l pp. 51–55, January–February, 1991. Original article submitted May 29, 1990. 相似文献
995.
Backinowsky LV Abronina PI Shashkov AS Grachev AA Kochetkov NK Nepogodiev SA Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(19):4412-4423
Glycosylation of sugar trityl ethers with sugar 1,2-O-(1-cyano)ethylidene derivatives (the trityl-cyanoethylidene condensation) has been applied to the synthesis of highly branched (dendritic) mannooligosaccharides incorporating a Manalpha1-->3(Manalpha1-->6)Man structural motif. The convergent synthetic strategy used to assemble these oligosaccharides was based on the use of glycosyl acceptors and/or a glycosyl donor already bearing this structural motif. The former were represented by mono- and ditrityl ethers of ManalphaOMe, Manalpha1-->3ManalphaOMe, and Manalpha1-->3(Manalpha1-->6)ManalphaX, where X=OMe or SEt. The pivotal glycosyl donor was the peracetylated 1,2-O-(1-cyano)ethylidene-3,6-di-O-(alpha-D-mannopyranosyl)-beta-D-mannopyranose (1), prepared by orthogonal Helferich glycosylation of the known 1,2-O-(1-cyano)ethylidene-beta-D-mannopyranose with tetra-O-acetyl-alpha-D-mannopyranosyl bromide followed by O-acetylation. Glycosylation of acetates of methyl 6-O-trityl-alpha-D-mannopyranoside and methyl 3,6-di-O-trityl-alpha-D-mannopyranoside with one equivalent of the donor 1 gave rise to the isomeric tetrasaccharide derivatives, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6ManalphaOMe and Manalpha1-->3(Manalpha1-->6)Manalpha1-->3ManalphaOMe, respectively. The latter derivative was further mannosylated at the remaining 6-O-trityl acceptor site to give the protected pentasaccharide Manalpha1-->3(Manalpha1-->6)Manalpha1-->3(Manalpha1-->6)ManalphaOMe. The isomeric pentasaccharide, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6(Manalpha1-->3)ManalphaOMe, was prepared by reaction of 1 with the 6-O-trityl derivative of (Manalpha1-->3)ManalphaOMe. In a similar fashion, 6'- and 6"-O-trityl derivatives of the branched trisaccharide Manalpha1-->3(Manalpha1-->6)ManalphaOMe served as precursors for two isomeric mannohexaosides. The 3,6-di-O-trityl ether of ManalphaOMe and the 6',6"-di-O-trityl ether of Manalpha1-->3(Manalpha1-->6)ManalphaX (X=OMe or SEt) were efficiently bis-glycosylated with the donor 1 to give the corresponding protected mannoheptaoside and mannononaoside. The yields of these glycosylations with the donor 1 ranged from 50 to 66 %. Final deprotection of all the oligosaccharides was straightforward and afforded the target products in high yields. Both the acylated and deprotected products were characterized, and the intersaccharide connectivities were elucidated by extensive one- and two-dimensional NMR spectroscopy. The described blockwise convergent approach allows assembly of a variety of 3,6-branched mannooligosaccharides. 相似文献
996.
A.?Ya.?NeimanEmail author N.?N.?Pestereva A.?R.?Sharafutdinov Yu.?P.?Kostikov 《Russian Journal of Electrochemistry》2005,41(6):598-611
The conduction and transport numbers of charge carriers for composites in the systems MeWO4-WO3 (Me = Ca, Sr, Ba) are studied as a function of the temperature and the activity of oxygen in a gas phase. The transport numbers are determined by an emf method and are estimated from dependences of conductance on the activity of oxygen in a gas phase. The deficiencies of the given procedure as applied to investigation of properties of composite phases are analyzed. The materials under study are classified with a class of metacomposites. The concentration intervals of the ionic, mixed, and electronic conductions are determined. The conduction of composites of compositions (100 − x)MeWO4 ⋅ xWO3 is predominantly ionic at x ≤ 10 (Me = Ca), x ≤ 60 (Me = Sr), and x ≤ 45 (Me = Ba). The obtained data are explained in the framework of a model that represents a composite as a distributed matrix system where a film of surface phase MeW-s with a high mobility of oxygen ions plays the role of a connected matrix. It is presumed that the surface phase MeW-s possesses double-sided surface activity (α MeW-s ≤
) and a higher mobility with respect to MeWO4 and WO3. The discovered anomalies of dependences
(T) and partial dependences
, σel(T) are explained by a change in the stoichiometry, morphology, and the degree of connectedness of surface phase MeW-s caused by with a change in the temperature and composition of composites.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 680–693.Original Russian Text Copyright © 2005 by Neiman, Pestereva, Sharafutdinov, Kostikov.Published on the basis of a report delivered at the VII Meeting on Fundamental Problems in Solid-State Ionics (Chernogolovka-2004). 相似文献
997.
We study the dynamics of tethered chains of length N on adsorbing surfaces, considering the dilute case; for this we use the bond fluctuation model and scaling concepts. In particular, we focus on the mean-square displacement of single monomers and of the center of mass of the chains. The characteristic time tau of the fluctuations of a free chain in a good solvent grows as tau approximately N(a), where the coefficient a obeys a=2nu+1. We show that the same coefficient also holds at the critical point of adsorption. At intermediate time scales single monomers show subdiffusive behavior; this concurs with the behavior calculated from scaling arguments based on the dynamical exponent a. In the adsorbed state tau(perpendicular), the time scale for the relaxation in the direction perpendicular to the surface, becomes independent of N; tau(perpendicular) is then the relaxation time of an adsorption blob. In the direction parallel to the surface the motion is similar to that of a two-dimensional chain and is controlled by a time scale given by tau(parallel) approximately N(2nu(2)+1)L(-2Delta(nu/nu)), where nu(2) is the Flory exponent in two dimensions, nu is the Flory exponent in three dimensions, and Deltanu=nu(2)-nu. For the motion parallel to the surface we find dynamical scaling over a range of about four decades in time. 相似文献
998.
A. K. Molodkin N. Ya. Esina M. V. Tachaev M. N. Kurasova 《Russian Journal of Inorganic Chemistry》2007,52(10):1567-1569
pH titration shows that 1 : 1 : 1 mixed-ligand complexes are formed in the systems palladium(II)-Cyt-Glu-H2O (loggB = 19.73) and palladium(II)-Cyt-Lys-H2O (logβ = 16.20). Complexes Pd(C5H5N5)(C5H8NO4)Cl, Pd(C5H5N5)(C6H13N2O2)Cl, Pd(C4H5N3O)(C6H13N2O2)Cl, and Pd(C4H5N3O)(C5H8NO4)Cl are synthesized and characterized by chemical analysis, X-ray powder diffraction, and thermogravimetry. The coordination mode of amino acids, cytosine, and adenine to the palladium(II) ion is determined. 相似文献
999.
(C2H10N2)[BPO4F2] — Strukturbeziehungen zwischen [BPO4F2]2— und [Si2O6]4— Colourless crystals of (C2H10N2)[BPO4F2] were prepared from mixture of ethylendiamine, H3BO3, BF3 · C2H5NH2, H3PO4 and HCl under mild hydrothermal conditions (220 °C). The crystal structure was determined by single crystal methods (triclinic, P1¯ (no. 2), a = 451.85(5) pm, b = 710.20(8) pm, c = 1210.2(2) pm, α = 86.08(1)°, β = 88.52(2)°, γ = 71.74(1)°, Z = 2) and contains infinite tetrahedral zweier‐single‐chains {[BPO4F2]2—} which are isoelectronic (48e—) with the polyanions {[Si2O6]4—} of the pyroxene family. 相似文献
1000.