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121.
Lancelot N Elbayed K Raya J Piotto M Briand JP Formaggio F Toniolo C Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1317-1323
A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis. 相似文献
122.
Josep Castells Elisabet Duñach Fernando Geijo Francisco López-Calahorra Margarita Prats Olga Sanahuja Laura Villanova 《Tetrahedron letters》1980,21(23):2291-2294
Triethylamine catalyzed Michael additions of benzoins to chalcone can prevail over the expected Michael-Stetter additions when certain thiazolium ion conjugate bases - prepared from the pertinent thiazolium salts and triethylamine- are used as catalysts. 相似文献
123.
Stefano Banfi Fernando Montanari Silvio Quici Gaguik Torossian 《Journal of inclusion phenomena and macrocyclic chemistry》1992,12(1-4):159-173
Reaction rates of alkene epoxidations, promoted by aqueous NaOCl and catalyzed by Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride1 (P) in the presence of a lipophilic axial ligand (L) (e.g.N-hexylimidazole) and carried out under H2O/CH2Cl2 two phase conditions at 0°C, are strongly enhanced by lowering the pH of the aqueous phase from 12.7 to 9.5. Under these conditions, a further relevant increase in the reaction rates can be achieved by adding phase-transfer catalysts (PT), e.g. quaternary ammonium salt 3, lipophilic crown ether4 or cryptand5, provided that the amount of L is very small (L/P=1 for very reactive alkenes, e.g. cyclooctene, and 10 for poorly reactive ones, e.g. 1-dodecene). In the case of cyclooctene epoxidation, the use of 0.006–0.03 mol. equiv. of PT completes the reaction in 1–10 min., the initial rates being up to 600 turnovers/min. with (2.2.2,C10) cryptand. In the absence of the axial ligand, the quaternary ammonium salt3 and cryptand5 show an inhibitory effect. Such an effect is due to the formation of the poorly reactive Mn(P)CI species, by Cl– extraction to the organic phase. However, dibenzo crown ether 4 does not show this effect. In the presence of 4, and with L/P =1, the 1-dodecene epoxidation reaches 94% in 1 min. The unique behavior of crown ethers can be explained by their ineffectiveness in extracting alkali chlorides, providing a very low concentration of Cl– in the organic phase and thus avoiding the Mn(III)-porphyrin deactivation.This paper is dedicated to the memory of the late Dr C. J. Pedersen. 相似文献
124.
German Urbina-Villalba Leonardo J. Rodriguez German R. Castro Fernando Ruette 《Journal of computational chemistry》1992,13(7):867-873
The electronic structure of cobalt silicide clusters Co7Si7 and Si7Co7 was studied in comparison to that of Co19 and Si17 clusters under the scope of the MINDO/SR method. Clusters Co7Si7 and Si7Co7 represent the environment of a cobalt atom and that of a silicon atom in the cobalt monosilicide bulk, respectively. It is found that the Co? Si bond is essentially sp in character with an indirect participation (by electrostatic interaction) of the cobalt d orbitals. Our calculations show a charge transfer from silicon to the d orbitals of cobalt via sp–sp interaction with an internal sp–d hybridization. The theoretical density of states for cobalt silicide clusters are reported and compared with experimental results of surface spectroscopies. © 1992 by John Wiley & Sons, Inc. 相似文献
125.
Fernando de Felice 《General Relativity and Gravitation》1991,23(2):135-149
In this paper we deduce the general pattern of the potential surfaces for time-like geodesics in the Curzon metric. We find that for fairly small energies and orbital angular momenta, the time-like geodesics group into two sets; the geodesics of one set tend to thez-axis asR=(r2+z2)1/2 0,R=0 being a directional singularity, the others tend to ther-axis. At low energies these two sets are detached but they merge together as the energy increases. Stable circular motion is confined to thez = 0-plane and an energy threshold for stationary motion exists and is equal (per unit of rest-mass energy) to 0.945, a value almost indistinguishable from that in the Schwarzschild space-time. 相似文献
126.
Yogiro Hama Fernando Silveira Navarra 《Zeitschrift fur Physik C Particles and Fields》1992,53(3):501-506
Transverse-momentum distributions of andK have been analyzed within a framework of the hydrodynamical model to obtain the
dependence of the collective transverse flow and the dissociation temperatureT
d inpp- and
-induced multiparticle production reactions. The main outcomes are the steadily increasing transverse flow and a slowly decreasingT
d as the incident energy increases. This behavior is in excellent agreement with early Landau's estimate. An extension of this to nucleus-nucleus collisions correctly gives account of the very soft component which has been observed in heavyion experiments. 相似文献
127.
We consider the zero-temperature behavior of a disordered array of quantum rotators given by the finite-volume Hamiltonian: $$H_\Lambda = - \mathop \Sigma \limits_{x \in \Lambda } \frac{{h(x)}}{2}\frac{{\partial ^2 }}{{\partial \varphi (x)^2 }} - J\mathop \Sigma \limits_{\left\langle {x,y} \right\rangle \in \Lambda } \cos (\varphi (x) - \varphi (y))$$ , wherex,y∈Z d , 〈,〉 denotes nearest neighbors inZ d ;J>0 andh={h(x)>0,x∈Z d } are independent identically distributed random variables with common distributiondμ(h), satisfying ∫h ?δ dμ(h)<∞ for some δ>0. We prove that for anym>0 it is possible to chooseJ(m) sufficiently small such that, if 0<J<J(m), for almost every choice ofh and everyx∈Z d the ground state correlation function satisfies $$\left\langle {\cos (\varphi (x) - \varphi (y))} \right\rangle \leqq C_{x,h,J} e^{ - m\left| {x - y} \right|} $$ for ally∈Z d withC x,h,J <∞. 相似文献
128.
Potential distribution and coupling parameter theories are combined to interrelate previous solvation thermodynamic results and derive several new expressions for the solvent reorganization energy at both constant volume and constant pressure. We further demonstrate that the usual decomposition of the chemical potential into noncompensating energetic and entropic contributions may be extended to obtain a Gaussian fluctuation approximation for the chemical potential plus an exact cumulant expansion for the remainder. These exact expressions are further related to approximate first-order thermodynamic perturbation theory predictions and used to obtain a coupling-parameter integral expression for the sum of all higher-order terms in the perturbation series. The results are compared with the experimental global solvation thermodynamic functions for xenon dissolved in n-hexane and water (under ambient conditions). These comparisons imply that the constant-volume solvent reorganization energy has a magnitude of at most approximately kT in both experimental solutions. The results are used to extract numerical values of the solute-solvent mean interaction energy and associated fluctuation entropy directly from experimental solvation thermodynamic measurements. 相似文献
129.
Jiménez JC Chavarría B López-Macià A Royo M Giralt E Albericio F 《Organic letters》2003,5(12):2115-2118
[reaction: see text] A solid-phase method for the synthesis of tentoxin has been developed. Two key steps-dehydration and N-alkylation-are carried out while the peptide is anchored to the resin. The method, which has been validated by the preparation of a library of tentoxin analogues, should be applicable to the generation of further libraries that have the tentoxin scaffold structure, as well as other structures containing N-alkylated didehydroamino acids. 相似文献
130.
Fernando Hernndez Flix L. Buenadicha Carmen Avendao Mnica Sllhuber 《Tetrahedron: Asymmetry》2002,12(24):3387-3398
An excess of base allows the regio- and diastereoselective alkylation at C(4) of the glycine templates 1-methyl(isopropyl)-2,4-dihydro-1H-pyrazino[2,1-b]quinazoline-3,6-diones 9a and 9b without the need for N(2)-protecting groups. While the alkylation of 9a gave exclusively the 1,4-anti-isomers, the isopropyl derivative 9b required much longer reaction times and occurred with lower diastereoselectivity. Fiscalin B 3 was obtained by alkylation of 9b with N-Boc-3-indolylmethyl bromide followed by indole deprotection. 相似文献