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61.
Gold-gold interactions in small polynuclear complexes are analysed using extended Hückel calculations. They are influenced by the nature of the ligand donor atoms, by the bridging ligands, but most by the formal oxidation state of the metal. Au---Au bonds are much stronger in complexes of Au(II) and Au(III), but a weak interaction between two d10 centres exists for Au(I) complexes, owing to mixing of the s and p orbitals with the d orbitals. Phosphines induce stronger metal-metal bonds when coordinated trans to the Au---Au bond in [Au(II)[(CH2)2PPh2]L]2 (Ph = phenyl), but have the opposite effect when bonded orthogonally to the metal-metal axis in Au(I) binuclear species. When two gold atoms are bridged by a single carbon atom, belonging either to mesityl (Mes = 2,4,6-Me3C6H2) or CR2, the former produces stronger Au(I)---Au(I) interactions, reflected in shorter distances. Formal oxidation states are proposed for the gold atoms in two mixed-valence clusters, [Au4(C6F5)2((PPh3)2CH})2(PPh3)2](ClO4)2 and [{(2,4,6-C6F3H2)Au(CH2PPh2CH2)2Au{in2-Au(CH2PPh2CH2)2Au](ClO4)2. The results suggest a higher oxidation state for the outer gold atoms, in both the T-shaped tetranuclear cluster and the Au6 linear chain. 相似文献
62.
[reaction: see text]. A very simple methodology to stereoselectively achieve tricyclic isonucleosides (nucleobase = thymine, uracil, and 5-fluoruracil) and 3'-C-branched nucleosides (nucleobase = theophylline) was performed by means of a DBU-mediated addition process using a readily available 2-bromo sugar. The mechanism for these transformations implies the loss of both substituents at C-2 and C-3 on the sugar moiety, and although it seems that DBU is probably involved, its involvement has not yet been ascertained. Cytosine did not react under these conditions. 相似文献
63.
Carmona D Lahoz FJ Atencio R Edwards AJ Oro LA Lamata MP Esteban M Trofimenko S 《Inorganic chemistry》1996,35(9):2549-2557
Treatment of the metallo ligands [ML(pz)(2)(Hpz)] (pz = pyrazolate; L = C(5)Me(5), M = Ir (1); L = mesitylene, M = Ru (3)) with [M'Cl{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (4), Ni (5)) yields heterodinuclear complexes of formula [LM(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (L = C(5)Me(5); M = Ir; M' = Co (6), Ni (7). L = mesitylene; M = Ru; M' = Co (8)). The related complex [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] (2) reacts with equimolar amounts of 4 or 5 to give mixtures of the corresponding bis(&mgr;-pyrazolato) &mgr;-chloro complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (9), Ni (10)) and the triply pyrazolato-bridged complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(3)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (11), Ni (12)). Complex 1 reacts with 5 in the presence of KOH to give the IrNi complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(3)Ni{HB(3-i-Pr-4-Br-pz)(3)}] (13) whereas its reaction with 4 and KOH rendered the bis(&mgr;-pyrazolato) &mgr;-hydroxo complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(2)(&mgr;-OH)Co{HB(3-i-Pr-4-Br-pz)(3)}] (14). The molecular structure of the heterobridged IrCo complex (6) and those of the homobridged RuNi (12) and IrNi (13) complexes have been determined by X-ray analyses. Compound 6 crystallizes in the monoclinic space group P2(1)/n, with a = 10.146(5) ?, b = 18.435(4) ?, c = 22.187(13) ?, beta = 97.28(4) degrees, and Z = 4. Complex 12 is monoclinic, space group P2(1), with a = 10.1169(7) ?, b = 21.692(2) ?, c = 11.419(1) ?, beta = 112.179(7) degrees, and Z = 2. Compound 13 crystallizes in the monoclinic space group Cc, with a = 13.695(2) ?, b = 27.929(6) ?, c = 13.329(2) ?, beta = 94.11(4) degrees, and Z = 4. All the neutral complexes 6, 12, and 13 consist of linear M.M'.B backbones with two (6) or three (12, 13) pyrazolate ligands bridging the dimetallic M.M' units and three substituted 3-i-Pr-4-Br-pz groups joining M' to the boron atoms. The presence in the proximity of the first-row metal M' of the three space-demanding isopropyl substituents of the pyrazolate groups induces a significant trigonal distortion of the octahedral symmetry, yielding clearly different M'-N bond distances on both sides of the ideal octahedral coordination sphere of these metals. 相似文献
64.
The global electrophilicity power, ω, of a series of dipoles and dipolarophiles commonly used in 1,3-dipolar cycloadditions may be conveniently classified within a unique relative scale. The effects of chemical substitution on the electrophilicity of molecules have been evaluated using a representative set of electron-withdrawing and electron-releasing groups for a series of dipoles including nitrone, nitrile oxide and azide derivatives. The absolute scale of electrophilicity is used to rationalize the chemical reactivity of these species as compared to the static reactivity pattern of the reagents involved in the Diels-Alder reactions. 相似文献
65.
Alvarez S Aullón G Fandos R García Fierro JL Ocón P Otero A Rojas S Terreros P 《Dalton transactions (Cambridge, England : 2003)》2005,(5):938-944
The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions. 相似文献
66.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献
67.
Luis A.?León Rafael?Notario Jairo?QuijanoEmail author Ederley?Vélez Claudia?Sánchez J. Camilo?Quijano Nouria?Al-Awadi 《Theoretical chemistry accounts》2003,110(6):387-394
Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002) 相似文献
68.
Ichimura AS Dye JL Camblor MA Villaescusa LA 《Journal of the American Chemical Society》2002,124(7):1170-1171
Electrides are materials in which alkali metals (Li through Cs) ionize to form bound alkali cations and "excess" electrons. The electrons reside in large cavities or channels or both in the host lattice. We report here the first synthesis of thermally stable inorganic electrides with cation-to-electron ratios of 1:1 as in organic electrides. Although alkali metal adducts to alumino-silicate zeolites are well known, the cation-to-electron ratio is generally 3:1 or greater because these zeolites contain alkali cations prior to incorporation of the alkali metal. In this work, two pure silica zeolites, ITQ-4and ITQ-7, with pore diameters of approximately 7 A, absorb up to 40 wt % cesium from the vapor phase (even at room temperature). The other alkali metals (except Li) can also be introduced at elevated temperatures. The optical and magnetic properties of the cesium-loaded samples suggest ionization to form Cs+ and e- with substantial electron-spin pairing. The metal-loaded samples are stable to at least 100 degrees C and are able to reduce small aromatic molecules such as benzene and naphthalene to the radical anions within the pores of the zeolite. 相似文献
69.
Briceo-Arias Luis Deride Julio Vega Cristian 《Journal of Optimization Theory and Applications》2022,192(1):56-81
Journal of Optimization Theory and Applications - In this paper, we propose a numerical approach for solving composite primal-dual monotone inclusions with a priori information. The underlying a... 相似文献
70.
Luis A. Caffarelli Cristian E. Gutié rrez 《Transactions of the American Mathematical Society》1996,348(3):1075-1092
In this paper we consider a family of convex sets in , , , , satisfying certain axioms of affine invariance, and a Borel measure satisfying a doubling condition with respect to the family The axioms are modelled on the properties of the solutions of the real Monge-Ampère equation. The purpose of the paper is to show a variant of the Calderón-Zygmund decomposition in terms of the members of This is achieved by showing first a Besicovitch-type covering lemma for the family and then using the doubling property of the measure The decomposition is motivated by the study of the properties of the linearized Monge-Ampère equation. We show certain applications to maximal functions, and we prove a John and Nirenberg-type inequality for functions with bounded mean oscillation with respect to