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911.
N-取代吩噻嗪和DDQ的电荷转移络合作用 总被引:1,自引:0,他引:1
具有盼嘤酸化学结构的化合物有广泛的用途I‘-\其中吩嘤埃衍生物在医学上用作抗精神病药物特别受到药理学家们的注意,发现其药理作用与其分子提供电子的能力有关卜‘」但是我们应该注意到,作为抗精神病药物的吩嚷嚷衍生物,其吩座爆分子的氮原子都连有一个叔胺基链问,例如氯丙障(I)和奋乃静(11).而我们知道,胺类特别是叔胺类有强的提供电子的能力*;在上述的药物分子中是主要的提供电子因素,因此以这类化合物作为给体研究其供电子能力,是不能实际反映吩嘤嗓分子本身的给电子能力的.吩嘤噪类属于二苯并杂环化合物,分子中既… 相似文献
912.
Ballesteros I. Ballesteros M. CabaÑas A. Carrasco J. MartÍn C. Negro M. J. Saez F. Saez R. 《Applied biochemistry and biotechnology》1991,(1):307-315
A total of 27 yeast strains belonging to the groupsCandida, Saccharomyces, andKluyveromyces were screened for their ability to grow and ferment glucose at temperatures ranging 32-45°C.
K. marxianus andK. fragilis were found to be the best ethanol producing organisms at the higher temperature tested and, so, were selected for subsequent
simultaneous saccharification and fermentation (SSF) studies. 相似文献
913.
对用调制差热分析(MDTA)准恒温法测样品热容量的情形进行了讨论。通过结合最基本的热传导定律和MDTA模型,指出了目前国际上测量样品热容量的准恒温法只能得到在所测温度范围内的物质热容量平均值,调制温度的幅度越大或调制频率越高,所得到的热容量数据越平滑。在所测温度范围内样品热容量基本不变时,用MDTA准恒温法较好;但当样品热容量在所测温度范围内有明显变化时,用传统差热分析法(DTA)更好一些。 相似文献
914.
Yannis Dotsikas 《Analytica chimica acta》2004,509(1):103-109
This study describes the employment of a novel imidazole-substituted phenol [4-(1-imidazolyl)phenol] as a highly potent signal enhancer in a horseradish peroxidase (HRP)-luminol chemiluminescence (CL) immunoassay. This competitive-type immunoassay for the model antigen fentanyl is based on the use of fentanyl polyclonal antibody immobilized on white microtiter plates and a biotinylated bovine serum albumin (BSA)-fentanyl derivative as a tracer. The latter was detected by means of streptavidin labeled with HRP, resulting in the generation of a high-intensity and relatively stable chemiluminescent signal, immediately after the addition of the substrate solution (NOAS). The developed method fulfilled the requirements of accuracy (percentage recovery ranged from 93.8 to 107%) and precision (intra- and inter-assay CVs were 2.5-5.2 and 4.5-11.9%, respectively). Its plasma detection limit (1.05 pg ml−1) was lower than those of previous immunoassays. The novel assay was compared in terms of sensitivity and concentration range with other common HRP substrate systems: luminol-p-iodophenol-H2O2 and TMB-H2O2. Finally, the described method was compared with an HRP-fentanyl conjugate-based assay, similar to commercially available kits (SKIT), employing the novel substrate solution for both assays and the differences observed were explained by applying previously described models. The detection limit was 4.82 pg ml−1 for SKIT, recovery values were 94.2-105% and intra- and inter-assay CVs were 2.5-5.2 and 4.5-11.9%, respectively. In conclusion, the proposed assay could be utilized for a wide range of molecules and replace the existing enzyme-labeled antigen-based kits. 相似文献
915.
Jessica L. Bender 《Tetrahedron》2004,60(34):7277-7285
Dibenzoylmethane (dbm) initiators with one and two alcohol sites were used to generate dbm end-functionalized and dbm-centered poly(ε-caprolactone) macroligands (dbmPCL and dbmPCL2) with low polydispersities (∼1.1). Chelation of polymeric ligands to metal ions (Eu3+, Fe3+, Ni2+ and Cu2+) produced metal-centered star polymers, which were characterized by UV-vis and fluorescence spectroscopy, as well as gel permeation chromatography. 相似文献
916.
Hermida-Ramón JM Brdarski S Karlström G Berg U 《Journal of computational chemistry》2003,24(2):161-176
An intramolecular NEMO potential is presented for the N-formylglycinamide molecule together with an intermolecular potential for the N-formylglycinamide-water system. The intramolecular N-formylglycinamide potential can be used as a building block for the backbone of polypeptides and proteins. Two intramolecular minima have been obtained. One, denoted as C5, is stabilized by a hydrogen bonded five member ring, and the other, denoted as C7, corresponds to a seven membered ring. The interaction between one water molecule and the N-formylglycinamide system is also studied and compared with Hartree-Fock SCF calculations and with the results obtained for some of the more commonly used force fields. The agreement between the NEMO and SCF energies for the complexes is in general superior to that of the other force fields. In the C7 region the surfaces obtained from the intramolecular part of the commonly used force fields are too flat compared to the NEMO potential and the ab initio calculations. We further analyze the possibility of using a charge distribution obtained from one conformation to describe the charge distribution of other conformations. We have found that the use of polarizabilities and generic dipoles can model most of the changes in charge density due to the different geometry of the new conformations, but that one can expect additional errors in the interaction energies that are of the order of 1 kcal/mol. 相似文献
917.
《Chemphyschem》2003,4(4):359-365
We studied the thermodynamic stability of a small monomeric protein, staphylococcal nuclease (Snase), as a function of both temperature and pressure, and expressed it as a 3D free‐energy surface on the p,T‐plane using a second‐order Taylor expansion of the Gibbs free‐energy change ΔG upon unfolding. We took advantage of a series of different techniques (small‐angle Xray scattering, Fourier‐transform infrared spectroscopy, differential thermal analysis, pressure perturbation calorimetry and densitometry) in the evaluation of the conformation of the protein and in evaluating the changes in the thermodynamic parameters upon unfolding, such as the heat capacity, enthalpy, entropy, volume, isothermal compressibility and expansivity. The calculated results of the free‐energy landscape of the protein are in good agreement with experimental data of the p,T‐stability diagram of the protein over a temperature range from 200 to 400 K and at pressures from ambient pressure to 4000 bar. The results demonstrate that combined temperature–pressure‐dependent studies can help delineate the free‐energy landscape of proteins and hence help elucidate which features and thermodynamic parameters are essential in determining the stability of the native conformational state of proteins. The approach presented may also be used for studying other systems with so‐called re‐entrant or Tamman loop‐shaped phase diagrams. 相似文献
918.
Chen Xiao-Ming Wu Yu-Luan Tong Ye-Xiang Sun Ziming David N. Hendrickson 《Polyhedron》1997,16(24):1041
A novel tetranuclear terbium(III) complex [Tb4(OH)4(pybet)6(H2O)8][Tb4(OH)4(pybet)6(H2O)7 (NO3)](ClO4)14·6H2O has been synthesized and shown by X-ray crystallography to have a cubane-like Tb4(μ3-OH)4(μ2-carboxylato-O,O′)6 core. The ligand pybet is pyridinoacetate, C5H5+N-CH2CO2−. Magnetic susceptibility data were measured for this Tb4 complex in the range of 2.0–320 K and in fields of 1.0 G to 50.0 kG. It is concluded that either there is very weak antiferromagnetic exchange interaction (J = −0.015 cm−1) or there is a small crystal-field splitting of the 7F6 TbIII ground state. 相似文献
919.
V. S. Lenenko P. Kränke M. Wahren V. B. Shur M. E. Vol'pin 《Russian Chemical Bulletin》1995,44(7):1293-1299
The interaction of labeled dinitrogen complexescis-(Me2PhP)4Mo(15N2)2 andtrans-(dppe)2W(15N2)2 with non-labeled nitronium and nitrosonium fluoroborates,14NO2BF4 and14NOBF4, in sulfolane at room temperature in the presence of H2SO4 results in rapid formation of labeled nitrous and nitric oxides (15N14NO,15NO), as well as15N14N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me2PhP)3Mo(15N2H2)Cl2 and (dppe)2W(15N2H2)Cl2, are capable of forming15N14NO,15NO, and15N14N under the action of14NO2BF4 and14NOBF4 in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995. 相似文献
920.
DFT calculations have been performed to determine the isomer shift for a series of iron(II) clusters with nitrogen-containing ligands which serve as models of coordination units in Fe(II) complexes with 1,2,4-triazoles possessing a 1 A 1 ? 5 T 2 spin transition. Good agreement has been found between the theoretical and experimental values of the isomer shift for both low-and high-spin phases. Our calculations confirmed the hypothesis about relationship between the experimentally observed differences in the isomer shift for the low-spin phases of the complexes and variations of the Fe-N mean bond length. 相似文献