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61.
Bhatt AI du Fou de Kerdaniel E Kinoshita H Livens FR May I Polovov IB Sharrad CA Volkovich VA Charnock JM Lewin RG 《Inorganic chemistry》2005,44(1):2-4
In situ EXAFS spectroscopic studies of uranium compounds in high temperature alkali chloride melts indicate the presence of oligomeric species. An investigation into UCl(3) and UCl(4) dissolved in LiCl reveals long range ordering of uranium atoms in the molten state which is not maintained on quenching. Studies of uranium dioxide dissolved in LiCl-KCl eutectic with HCl exhibit long range ordering in both molten and quenched states, and the EXAFS data can be modeled using multiple coordination shells. 相似文献
62.
RGDS‐ and SIKVAVS‐Modified Superporous Poly(2‐hydroxyethyl methacrylate) Scaffolds for Tissue Engineering Applications 下载免费PDF全文
Hana Macková Zdeněk Plichta Vladimír Proks Ilya Kotelnikov Jan Kučka Helena Hlídková Daniel Horák Šárka Kubinová Klára Jiráková 《Macromolecular bioscience》2016,16(11):1621-1631
Three‐dimensional hydrogel supports for mesenchymal and neural stem cells (NSCs) are promising materials for tissue engineering applications such as spinal cord repair. This study involves the preparation and characterization of superporous scaffolds based on a copolymer of 2‐hydroxyethyl and 2‐aminoethyl methacrylate (HEMA and AEMA) crosslinked with ethylene dimethacrylate. Ammonium oxalate is chosen as a suitable porogen because it consists of needle‐like crystals, allowing their parallel arrangement in the polymerization mold. The amino group of AEMA is used to immobilize RGDS and SIKVAVS peptide sequences with an N‐γ‐maleimidobutyryloxy succinimide ester linker. The amount of the peptide on the scaffold is determined using 125I radiolabeled SIKVAVS. Both RGDS‐ and SIKVAVS‐modified poly(2‐hydroxyethyl methacrylate) scaffolds serve as supports for culturing human mesenchymal stem cells (MSCs) and human fetal NSCs. The RGDS sequence is found to be better for MSC and NSC proliferation and growth than SIKVAVS.
63.
King BT Körbe S Schreiber PJ Clayton J Nemcova A Havlas Z Vyakaranam K Fete MG Zharov I Ceremuga J Michl J 《Journal of the American Chemical Society》2007,129(43):12960-12980
The 15 symmetrically methylated derivatives of the CB11H12(-) anion (1a) have been synthesized and found to vary greatly in ease of oxidation. Cyclic voltammetry in liquid SO2 yielded fully reversible oxidation potentials for five of those that have no adjacent unsubstituted vertices in positions 7-12; three others showed some indication of reversibility. The anions 1a-16a and the Jahn-Teller distorted neutral radicals 1r-16r have been characterized by ab initio and density functional theory calculations. In the state average CASSCF(13,12)/6-31+G* approximation, the ground state potential energy surface of 1r contains five symmetry-related pairs of minima. The computational results account for the reversible redox potentials very well when the solvent is included explicitly (RI-DFT(BP)/TZVP, COSMO). For display and for a semiquantitative understanding of methyl substituent effects in terms of perturbation theory, the molecular orbitals of 1a have been expressed in the symmetry-adapted cluster basis. The results serve as an underpinning for a set of additive empirical increments for redox potential prediction. Relative to the usual hydrogen standard, a single methyl group facilitates oxidation by approximately 50, 70, 70, and 10 mV in positions 1, 2, 7, and 12, respectively. This electron donor effect on the redox potential is due to a contribution, whereas those of (inductive and direct field) type are negligible. 相似文献
64.
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66.
Artur Vashurin Vladimir Maizlish Ilya Kuzmin Oleg Petrov Mikhail Razumov Svetlana Pukhovskaya Oleg Golubchikov Oscar Koifman 《Journal of inclusion phenomena and macrocyclic chemistry》2017,87(1-2):37-43
The influence of the size of conjugated π-system on catalytic activity of cobalt complex with β-octaphenylporphyrin and its tetraaza-, tetrabenzo and tetrabenzotetraaza derivatives was studied in present work. It is found that catalytic activity for oxidation of sulfur-containing compounds increases under extension of conjugated macrocycle system according to the following series CoP < CoBP ≤ CoPz < CoPPz ? CoPc. 相似文献
67.
I. A. Novakov L. L. Brunilina A. A. Vernigora I. A. Kirillov A. S. Mkrtchyan M. B. Navrotskii D. S. Sheikin A. S. Yablokov E. A. Ruchko V. V. Kachala 《Russian Journal of Organic Chemistry》2017,53(12):1844-1850
The aminolysis of 6-[1-(2,6-difluorophenyl)cyclopropyl]-5-methyl-2-(nitroamino)pyrimidin-4(3H)-one with various amines in butan-1-ol and under solvent-free conditions is successful when the amino group in the reagent is sterically unshielded and the reaction medium is characterized by a high dielectric permittivity. Reactions of the title compound with sterically shielded amines are accompanied by alcoholysis where the amine acts as a base catalyst. 相似文献
68.
Ilya I. Moiseev Tatiana A. Stromnova Irina N. Busygina Natalya Yu. Tihonova Natalya Yu. Kozitsyna Arkady M. Ellern Mikhail Yu. Antipin Yury T. Struchkov 《Journal of Cluster Science》1992,3(4):411-421
Thermolysis of tetranuclear palladium clusters Pd4(-Q)4 Pd4(-Q)4(-O2CR)4 (Q=CPh2 or CO;R=Me, CMe3, Ph, CH2Cl or CF3) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO2 insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)2(PPh3)]2 with HCO2H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh3 ligand to the palladium atom. The structure of the complex formed, [Pd(-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis. 相似文献
69.
An implicit account of the solvent effect can be carried out using traditional static quantum chemistry calculations by applying an external electric field to the studied molecular system. This approach allows one to distinguish between the effects of the macroscopic reaction field of the solvent and specific solute–solvent interactions. In this study, we report on the dependence of the simulation results on the use of the polarizable continuum approximation and on the importance of the solvent effect in nonpolar solvents. The latter was demonstrated using experimental data on tautomeric equilibria between the pyridone and hydroxypyridine forms of 2,6-di-tert-butyl-4-hydroxy-pyridine in cyclohexane and chloroform. 相似文献
70.
Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported. 相似文献