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21.
多电解质溶液中带电胶体粒子的电势分布由球形Poisson-Boltzmann方程(PBE)描述.PBE是一个非线性的微分方程,且难以求得其解析解.本文采用非线性P-B积分方程,计算电势分布的数值解.首先,根据静电场和热力学系统中的物理定理,导出描述电势分布的P-B积分方程(PBIE);其次,用迭代方法求PBIE的数值解.最后,计算了在3-1型电解液中无量纲半径κa分别为0.12和0.22,无量纲表面电势ξ分别为1,2,4,6时球形胶体粒子外部的电势值.为了检验数值解的精度,计算了表面电荷密度,并与Loeb(1961)和Oshima(1995)等人的结果比较,本文结果的相对误差小于1%,优于Oshima的结果. 相似文献
22.
无机层状复合氢氧化物中顺铂-DNA模型分子的选择性插入 总被引:5,自引:0,他引:5
药物分子的选择性包裹和控制释放是药物研究领域中具有挑战性的研究方向。本文研究表明:顺铂-DNA模型分子cis-[Pt(NH3)2(5′-GMP)2](5′-GMP 5′-单磷酸鸟苷)可插入无机层状复合氢氧化物[Zn0.68Al0.32(OH)2](NO3)0.32·mH2O。但另一种层状复合氢氧化物[LiAl2(OH)6]Cl·H2O由于其阳离子层中正电荷密度较高、阳离子层与层间阴离子之间静电作用较强,因而顺铂-DNA模型分子不能通过离子交换方式插入其层间。光谱数据证实插入层间的顺铂-DNA模型分子结构不变。这可能为铂-DNA分子的传递提供新的方法。 相似文献
23.
Hideki Nishimori Masahiro Tatsumisago Tsutomu Minami 《Journal of Sol-Gel Science and Technology》1997,9(1):25-31
Monodispersed silica particles up to ca. 1.2 μm in diameter were prepared by hydrolysis of tetraethoxysilane in the presence
of sodium dodecyl sulfate (SDS). The particle size was increased with an increase of SDS added. The geometrical standard deviation
of the particles was decreased with an increase of SDS. In the earlier reaction stage, double spherical particles by the coalescence
of the particles were frequently observed when large amounts of SDS were added. Particle size was gradually increased after
the coalescence occurred and spherical particles were finally obtained. The results of Nielsen’s chronomal analysis suggest
that the polynuclear layer growth took place after the coalescence of the particles in the presence of larger amount of SDS. 相似文献
24.
Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides 总被引:1,自引:0,他引:1
J.M. García-García M.E. Prez-Bernal R.J. Ruano-Casero V. Rives 《Solid State Sciences》2007,9(12):1115-1125
Layered double hydroxides with the hydrotalcite-like structures, containing Mg2+ and Al3+, doped with Cr3+ and Y3+, have been prepared by precipitation at constant pH. The weight percentages of Cr3+ and Y3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV–vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at −196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE – L*a*b*) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments. 相似文献
25.
通过流动相中电解质浓度对毛细管电色谱柱效能的流动相平均线速度的影响,研究了CEC中双电层叠加现象。提出选择合适电解质组成的浓度及在制备色谱柱过程中避免细小和破碎的固定相颗粒进入柱中,以有效地减小双电层叠加作用。 相似文献
26.
V. A. Livshits B. G. Dzikovskii V. P. Tsybyshev B. B. Meshkov 《Russian Chemical Bulletin》1996,45(7):1563-1571
Isotherms of the binding of dodecyl sulfate anions (DDS–)and Na+ counterions during their coadsorption with a nonionic polymer. proxanol (PR). at the interface of dodecane-water emulsions have been measured by conductometry and Na-selective potentiometry. The adsorption of DDS– and PR is concurrent. The affinity constant of PR to the interface determined by the Langmuir model decreases as the concentration of PR increases, and the surface concentration of DDS– tends to a nonzero limiting value at high concentrations of PR. The surface (o) and electrokinetic () potentials at the interface have been determined at various polymer concentrations by the spin probe and electrophoresis methods. The average dielectric permeability and density of polymer segments in We adsorption layer have been determined by ESR. The lower boundary of the hydrodynamic thickness of the polymer adsorption layer at the interface has been estimated from the dependences of o and on the ionic strength.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1653–1661, July, 1996. 相似文献
27.
Òscar Rubio-Pons Boris Minaev Oleksandr Loboda Hans Ågren 《Theoretical chemistry accounts》2005,113(1):15-27
The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet–triplet (3B1u1Ag) transition through a number of vibronic subbands. The second order spin–orbit coupling (SOC) contribution to the spin splitting of the 3B1u (3*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin–spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet–singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.Acknowledgment O. R.-P. would like to thank the European MOLPROP network for support. The authors thank Alexander Baev for fruitful discussions. This work was supported by the Swedish Royal Academy of Science (KVA). 相似文献
28.
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
29.
A background-free, fast protein staining method in polyacrylamide gel electrophoresis using an acidic dye, zincon (ZC) and a basic dye, ethyl violet (EV) is described. It is based on the counterion dye staining technique that employs two oppositely charged dyes to form an ion-pair complex in staining solution. The selective binding of free dye molecules to proteins in acidic solution produces bluish violet-colored bands. It is a rapid and end-point staining procedure, involving only fixing and staining steps that are completed in 1-1.5 h. The detection limit of this method is 8-15 ng of protein that is comparable to the sensitivity of the colloidal Coomassie Brilliant Blue G (CBBG) stain. Due to its sensitivity and speed, this stain may be more practical than any other dye-based stains for routine laboratory purposes. 相似文献
30.
Effects of double substitution on the thermodynamic stabilities of nitrogen radicals 总被引:1,自引:0,他引:1
Studiesonkineticsofradicalreactions[1]andonCHbonddissociationenergies(BDE)[2]haveshownthatcarbonradicalsarestabilizedbyeitheranelectrondonatinggroup(EDG)oranelectronwithdrawinggroup(EWG),andthatifacarbonradicalissubstitutedwithbothanEDGandanEWGatthesamecen… 相似文献