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61.
H2CCF自由基与HNCO反应机理的理论研究 总被引:4,自引:0,他引:4
采用密度泛函理论的B3LYP方法, 在6-311++G(d,p)基组水平上研究了H2CCF自由基与HNCO的微观反应机理, 优化了反应过程中的反应物、中间体、过渡态和产物, 为了获得更精确的能量信息, 还在QCISD(T)/6-311++G(d,p)基组水平上计算了各物质的能量.振动分析结果和IRC分析结果证实了中间体和过渡态的真实性, 计算所得的成键临界点电荷密度的变化也确认了反应过程.对于H2CCF自由基与HNCO反应, 我们找到了六条可行的反应通道, 结果分析表明通道H2CCF+HNCO→IM3→TS5→H2CCFH+NCO控制步骤活化能最低, 是该反应的主要通道, 在此反应过程中有稳定的氢键复合物IM3生成, 还表现出氢原子迁移的反应特征. 相似文献
62.
Malhotra E. Kaushik N. K. Sodhi G. S. 《Journal of Thermal Analysis and Calorimetry》2002,68(1):215-222
A number of ionic chelate complexes of maltol(A) and hafnium(IV) the type[(η5−C5H5)2HfL]+[MCl3]− (B) [HL=maltol; M=Zn(II), Cd(II), Hg(II), Cu(II)]have been synthesized and characterized by spectral studies (IR, UV, 1H NMR and 13C NMR). The stoichiometry of the complexes has been confirmed by conductance measurements. Thermogravimetric (TG) and differential
thermal analytical (DTA) studies have been carried out for these complexes and from TG curves, the order, apparent activation
energy and apparent activation entropy of the thermal decomposition reactions have been elucidated .The order in each case
has been determined to be one and the degree of spontaneity and lability have been inferred from the apparent activation energy
and entropy, respectively. Thermal parameters have been correlated with some structural aspects of the complexes concerned.
From differential thermal analysis curves, the heat of reaction has been calculated.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
63.
Radoslav D. Mii Radmila P. Marinkovi-Neduin Zoltán Schay István Nagy Jelena S. Kiurski Ern E. Kiss 《Reaction Kinetics and Catalysis Letters》2007,91(1):85-92
Investigations of a commercial NiMo/Al2O3 hydrodesulfurization (HDS) catalyst are directed towards optimization of the activation procedure of HDS catalyst concerning
active phase formation and thermal stability. Structural and textural data obtained with XRD, IR-FTIR, XPS and LTNA reveal
that the optimal temperature for the formation of active species on the catalyst surface and an appropriate pore structure
is 300°C. 相似文献
64.
E. T. Denisov 《Russian Chemical Bulletin》2004,53(8):1602-1608
The transition state of addition of free radicals and atoms to multiple bonds is considered as a result of intersecting of two parabolic potential curves. One of them characterizes the stretching vibration of the attacked multiple bond, and another curve characterizes the stretching vibration of the bond formed in the transition state. The force constant of the latter is calculated by an empirical equation that correlates the force constant with the bond dissociation energy. In the framework of this model, the thermally neutral activation energy (E
e0) and the elongation of the attacked and formed bonds (r
e) in the transition state were calculated from the experimental data (activation energy (E
e) and enthalpy of reaction (H
e)) for the addition of an H atom and methyl, alkoxyl, aminyl, triethylsilyl, and peroxyl radicals to the C=C bond and the addition of H and CH3 to the C=O and CC bonds. Analysis of the data obtained showed that E
e0 depends linearly on the |H
e| + Ee sum, i.e., Ee0/kJ mol–1 = 14.2 + 0.61 · (Ee – H
e), and the bond elongation in the transition state for addition of the most part of radicals to ethylene and acetylene vary within (0.65–0.87)·10–10 m. The factors affecting the activation energy of the radical addition reactions are discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1542–August, 2004. 相似文献
65.
Flash vacuum pyrolysis (fvp) of some substituted [1,2,4]triazolo[3,4-c][1,2,4]benzotriazine derivatives (1a-d) has been studied between 450 and 600 °C. The only transformation observed up to 525 °C was the unexpected valence bond isomerization of the angularly fused starting compounds to the isomeric linearly fused [1,2,4]triazolo[4,3-b][1,2,4]benzotriazine derivatives (9a-d), whereas at higher temperatures fragmentation products such as aromatic nitriles were also formed. Kinetic measurements revealed negative entropies of activation in the isomerization process, which suggest a concerted ring closure reaction to an intermediate antiaromatic diazirine. Reversibiblity of the title isomerization reaction was also proved by FVP experiments. 相似文献
66.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
67.
Low molecular weight poly(dimethylsiloxane) and poly(methylphenylsiloxane) were synthesized and blended with polyimide (PI) at its precursor poly(amic acid) stage. FTIR analysis has proven the retention of polysiloxanes in polyimide after the ultimate curing of blends. Differential scanning calorimetric analysis was performed on polysiloxanes to elucidate the structures present in polymers while thermogravimetric analysis (TGA) was performed on polysiloxanes, polyimide as well as their blends to evaluate the thermal stability and to analyze the effect of polysiloxane incorporation in blends. Blends have shown synergistic improvement as compared to neat polyimide. 相似文献
68.
CO2部分氧化乙烷制乙烯Pd—Cu/MoO3—SiO2催化剂的研究 总被引:7,自引:0,他引:7
用化学吸附-红外光谱、化学吸附-程序升温脱附(TPD)和微型反应技术研究了Pd-Cu/MoO3-SiO2(MoSO)催化剂对CO2和乙烷的吸附活化和部分氧化反应性能.结果表明,乙烷以C—H键中的H吸附于MoSO载体表面MoO键的端基氧上;Pd-Cu/MoSO催化剂对CO2有良好的化学吸附活化性能,CO2的吸附除有线式吸附态和剪式吸附态外,还有一种新的卧式吸附态;Pd-Cu/MoSO催化剂的晶格氧参与了化学反应.探讨了在Pd-Cu/MoSO催化剂上CO2的部分氧化乙烷反应机理 相似文献
69.
Poly(N-isopropylacrylamide) (PNIPAM) has a low critical solution temperature (LCST) at 32°C in water and the hydrophilicity changes through the LCST. The microspheres whose surface was composed of PNIPAM exhibited phase transition behavior around 32°C. Therefore, the interactions between PNIPAM micropheres and granulocytes depended on the temperature. That is, the oxygen consumption and active oxygen production by cells in contact with PNIPAM-containing microspheres and adhesion of the microspheres to the cell surface were more enhanced above the LCST of PNIPAM than below it, whereas no significant temperature dependence of cell–microspheres interaction was observed in nonthermosensitive microsphere systems. It was suggested that the function of cells could be controlled with temperature using the temperature-sensitive microspheres. 相似文献
70.
Yu. A. Borisov Yu. A. Zolotarev E. V. Laskatelev N. F. Myasoedov 《Russian Chemical Bulletin》1997,46(3):407-409
The simplest quantum-chemical models of hydrogen spillover over a graphite-like surface as a proton or radical have been considered.
The condensed planar C24H12 molecule was used as a model surface. Theab initio calculations of the interaction of hydrogen with the model surface were carried out by the restricted Hartree-Fock (HF) method
in the STO-3G and 6-31 G* basis sets. The radical hydrogen can not bind to such a surface, whereas the proton binds to it with an energy release of
186 kcal mol−1. The activation energy of the transfer of the proton between two neighboring carbon atoms (10 kcal mol−1) has been determined. The simplest model of the hydrogen migration as a proton over the model surface can be used for describing
the spillover of hydrogen over the graphite surface.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 428–430, March, 1997. 相似文献