全文获取类型
收费全文 | 4928篇 |
免费 | 98篇 |
国内免费 | 13篇 |
专业分类
化学 | 2460篇 |
晶体学 | 131篇 |
力学 | 228篇 |
数学 | 687篇 |
物理学 | 1533篇 |
出版年
2022年 | 55篇 |
2021年 | 72篇 |
2020年 | 77篇 |
2019年 | 89篇 |
2018年 | 68篇 |
2017年 | 87篇 |
2016年 | 129篇 |
2015年 | 105篇 |
2014年 | 128篇 |
2013年 | 349篇 |
2012年 | 239篇 |
2011年 | 263篇 |
2010年 | 167篇 |
2009年 | 159篇 |
2008年 | 198篇 |
2007年 | 216篇 |
2006年 | 167篇 |
2005年 | 173篇 |
2004年 | 138篇 |
2003年 | 95篇 |
2002年 | 91篇 |
2001年 | 68篇 |
2000年 | 52篇 |
1999年 | 52篇 |
1998年 | 50篇 |
1996年 | 54篇 |
1995年 | 48篇 |
1994年 | 57篇 |
1993年 | 71篇 |
1992年 | 64篇 |
1991年 | 48篇 |
1990年 | 58篇 |
1989年 | 53篇 |
1988年 | 63篇 |
1987年 | 51篇 |
1986年 | 30篇 |
1985年 | 73篇 |
1984年 | 96篇 |
1983年 | 57篇 |
1982年 | 63篇 |
1981年 | 70篇 |
1980年 | 71篇 |
1979年 | 72篇 |
1978年 | 68篇 |
1977年 | 62篇 |
1976年 | 57篇 |
1975年 | 44篇 |
1974年 | 47篇 |
1973年 | 55篇 |
1972年 | 34篇 |
排序方式: 共有5039条查询结果,搜索用时 375 毫秒
831.
Universal electro-osmosis formulae for porous media 总被引:1,自引:0,他引:1
Approximate analytical formulae valid for any porous media with elongated pores are derived for the electro-osmotic coefficient alpha and for the average ionic concentration n . A macroscopic Debye-Hückel length kappa (-)(-1) based on n is introduced. Simultaneously, the electro-osmotic coefficient alpha is systematically calculated for various media, zeta potentials and electrolyte concentrations by solving the local equations. Numerical results show that kappa (-)(-1) and alpha follow universal curves valid whatever the porous medium; these curves can be approximated by the analytical formulae previously derived. These formulae can be used to provide a priori estimates of the electro-osmotic coefficient. 相似文献
832.
Adsorption of basic fuchsin using waste materials--bottom ash and deoiled soya--as adsorbents 总被引:1,自引:0,他引:1
Basic fuchsin, a triaminotriphenylmethane dye, was removed by adsorption utilizing two waste materials--"bottom ash," a power plant waste material, and "deoiled soya," an agriculture waste product. The adsorbents were characterized through IR spectroscopy and differential thermal analysis (DTA). Batch adsorption experiments were carried out by measuring effects of pH, adsorbate concentration, sieve size, amount of adsorbent, contact time, temperature, etc. The results have been verified on the basis of Langmuir and Freundlich adsorption isotherm models and data obtained have been applied to calculate thermodynamic parameters. Specific rate constants for the processes were calculated by kinetic measurements and a pseudo-second-order adsorption kinetics was observed in each case. To identify whether the ongoing process is particle diffusion or film diffusion, the treatment given by Boyd and Reichenberg was employed. To assess the practical utility of the adsorbent, the aqueous adsorbate samples were eluted through fixed-bed columns of respective adsorbents. Attempts were also made to recover the adsorbed dyes by passing suitable solvent through the columns. 相似文献
833.
Singh L Ishar MP Elango M Subramanian V Gupta V Kanwal P 《The Journal of organic chemistry》2008,73(6):2224-2233
Thermal and microwave assisted [4+2] cycloadditions of 1,4-diaryl-1-aza-1,3-butadienes with allenic esters lead to cycloadducts, which after a 1,3-H shift afford variedly substituted unsymmetrical 2-alkyl-1,4-diaryl-3-ethoxycarbonyl-1,4-dihydropyridines in high yields. Reactions carried out under microwave irradiation are cleaner and give higher yields with much shortened reaction times. Density functional theory (DFT) at the B3LYP/6-31G* level has been used to calculate geometric features of the reactants, barrier for s-trans to s-cis and reverse isomerization of azadienes (5a-d, 10a-e), dihedral angles between N(1), C(2), C(3), and C(4) atoms of azadienes along with various indices such as chemical hardness (eta), chemical potential (micro), global electrophilicity (omega), and the difference in global electrophilicity (Deltaomega) between the reacting pairs and Fukui functions (f (+) and f(-)). The results revealed that s-trans is the predominant conformation of azadienes at ambient temperature and the barrier for conversion of the s-trans rotamer of 1-azadienes to s-cis may be the major factor influencing the chemoselectivity, i.e., [4+2] verses [2+2] cycloaddition. The regiochemistry of the observed cycloadditions is collated with the obtained local electrophilicity indices (Fukui functions). Transition states for the formation of both [4+2] and [2+2] cycloadducts as located at the PM3 level indicate that the transition state for the formation of [4+2] cycloadducts has lower energy, again supporting the earlier conclusion that preferred formation of [4+2] cycloaaducts at higher temperature may be a consequence of barrier for s-trans to s-cis transformation of 1-azadienes. 相似文献
834.
Somnath Roy Tarak Nath Mandal Anil Kumar Barik Samik Gupta Ray J. Butcher Mohamed Salah El Fallah Javier Tercero Susanta Kumar Kar 《Polyhedron》2008
The synthesis and structure of a pyrazole-based orthogonal ferromagnetically coupled tetracopper(II) 2 × 2 homoleptic grid complex [Cu4(PzOAPyz)4(ClO4)2](ClO4)2 · 6H2O (1), formed by the reaction between the ditopic ligand PzOAPyz and Cu(ClO4)2 · 6H2O, are described. The ligand contains terminal pyrazole and pyrazine residues bound to a central flexible diazine subunit (N–N) as well as one potentially bridging alkoxo group. The two adjacent metal centers are linked by an alkoxo oxygen forming essentially a square Cu4(μ-O4) cluster. In the Cu4(μ-O4) core, out of the four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by one of the oxygen atoms of a coordinated perchlorate ion. Complex 1 has been characterized structurally and magnetically. Although the large Cu–O–Cu bridge angles (137–138°) and short Cu–Cu distances (3.964–3.970 Å) are suitable for the transmission of the expected antiferromagnetic coupling, the square-based Cu4(μ-O4) cluster exhibits an intramolecular ferromagnetic exchange (J = 7.47 cm−1) between the metal centers with an S = 2 magnetic ground state associated with the quasi orthogonal arrangement of the magnetic orbitals (dx2-y2). The exchange pathway parameters have been evaluated from density functional calculations. 相似文献
835.
The metal complexes of N, N′‐bis (o‐hydroxy acetophenone) propylene diamine (HPPn) Schiff base were supported on cross‐linked polystyrene beads. The complexation of iron(III), copper(II), and zinc(II) ions on polymer‐anchored HPPn Schiff base was 83.4, 85.7, and 84.5 wt%, respectively, whereas the complexation of these metal ions on unsupported HPPn Schiff base was 82.3, 84.5, and 83.9 wt%. The iron(III) complexes of HPPn Schiff base were octahedral in geometry, whereas copper(II) and zinc(II) ions complexes were square planar and tetrahedral. Complexation of metal ions increased the thermal stability of HPPn Schiff base. Catalytic activity of metal complexes was tested by studying the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The polymer‐supported HPPn Schiff base complexes of iron(III) ions showed 73.0 wt% conversion of phenol and 90.6 wt% conversion of cyclohexene at a molar ratio of 1:1:1 of substrate to catalyst and hydrogen peroxide, but unsupported complexes of iron(III) ions showed 63.8 wt% conversion for phenol and 83.2 wt% conversion for cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 and 98.3 wt%, respectively with supported HPPn Schiff base complexes of iron(III) ions but was lower with HPPn Schiff base complexes of copper(II) and zinc(II) ions. Activation energy for the epoxidation of cyclohexene and phenol conversion with unsupported HPPn Schiff base complexes of iron(III) ions was 16.6 kJ mol?1 and 21.2 kJ mol?1, respectively, but was lower with supported complexes of iron(III) ions. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
836.
Huajun Yuan Cynthia J. Jameson Sumnesh K. Gupta James D. Olson Sohail Murad 《Fluid Phase Equilibria》2008,269(1-2):73-79
Using the molecular dynamics (MD) method, we demonstrate that intermolecular nuclear magnetic resonance (NMR) chemical shifts can be used to evaluate and develop intermolecular potentials for cross-interactions for use in solubility studies. The calculation of chemical shifts in MD is an order of magnitude more efficient than solubilities, which makes it an attractive tool for fine-tuning potential models. We examine the average Xe chemical shifts in cyclo-alkanes over a range of temperatures to develop a suitable potential model for the cross-interactions between Xe and a series of cyclo-alkanes. Our results clearly demonstrate that potential models that show better agreement with experiments for chemical shift, invariably lead to better agreement with experiment for Henry's constant and solubility of gases in solvents. 相似文献
837.
Agrawal M Pich A Gupta S Zafeiropoulos NE Simon P Stamm M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(3):1013-1018
Sub-micrometer-sized hollow tantalum oxide (Ta2O5) spheres with tunable shell thickness and void size have been fabricated exploiting beta-diketone-functionalized polystyrene (PS) beads as sacrificial templates in a sol-gel process. First, a controlled precipitation of Ta2O5 nanoparticles was carried out on the template surface by hydrolyzing tantalum ethoxide (Ta(OEt)5) at room temperature, and subsequently, the polymer core was removed either via chemical treatment with toluene or calcination at 650 degrees C. The thickness of the tantala shell precipitated on the PS core during the coating process was tuned between 100 and 142 nm by varying the concentration of tantala precursor in the reaction media. The obtained Ta2O5-coated PS particles and hollow microspheres were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Due to the unique optical and dielectric properties, these nanostructured materials are envisaged to be used in applications such as novel building blocks for the fabrication of advanced materials, surface coatings, catalysts, and drug delivery systems. 相似文献
838.
Industrial wastewaters containing heavy metals pose a major environmental problem that needs to be remedied. The present study reports the ability of two non-living (dried) fresh water algae, Oedogonium sp. and Nostoc sp. to remove lead(II) from aqueous solutions in batch system under varying range of pH (2.99-7.04), contact time (5-300 min), biosorbent dose (0.1-0.8 g/L), and initial metal ion concentrations (100 and 200mg/L). The optimum conditions for lead biosorption are almost same for the two algal biomass Oedogonium sp. and Nostoc sp. (pH 5.0, contact time 90 and 70 min, biosorbent dose 0.5 g/L and initial Pb(II) concentration 200mg/L) however, the biomass of Oedogonium sp. was found to be more suitable than Nostoc sp. for the development of an efficient biosorbent for the removal of lead(II) from aqueous solutions, as it showed higher values of q(e) adsorption capacity (145.0mg/g for Oedogonium sp. and 93.5mg/g for Nostoc sp.). The equilibrium data fitted well in the Langmuir isotherms than the Freundlich isotherm, thus proving monolayer adsorption of lead on both the algal biomass. Analysis of data shows that the process involves second-order kinetics and thermodynamic treatment of equilibrium data shows endothermic nature of the adsorption process. The spectrum of FTIR confirms that the amino and carboxyl groups on the surface of algal biomass were the main adsorption sites for lead removal. Both the biosorbents could be regenerated using 0.1 mol/L HCl solution, with upto 90% recovery. The biosorbents were reused in five biosorption-desorption cycles without a significant loss in biosorption capacity. Thus, this study demonstrated that both the algal biomass could be used as an efficient biosorbents for the treatment of lead(II) bearing wastewater streams. 相似文献
839.
Raj Kumar Gupta K.A. Suresh 《Colloids and surfaces. A, Physicochemical and engineering aspects》2008,320(1-3):233-239
The self-assembled monolayer of the thiocholesterol (TCh) exhibits interesting properties that can be used for various technological applications. TCh is predominantly a hydrophobic molecule, and it does not spread at the air–water interface to form a stable Langmuir monolayer. We have stabilized the TCh molecules in the cholesterol (Ch) monolayer. We find the mixed monolayer to be stable upto 0.75 mole fraction of TCh in Ch. The mixed monolayer shows an initial and a final collapse. On compressing the monolayer beyond the initial collapse, the TCh molecules squeeze out irreversibly from the mixed monolayer phase. The calculation of excess area per molecule for the TCh and Ch mixed monolayer system indicates an attractive interaction between the component molecules. Interestingly, the elasticity of the Ch monolayer reduces to less than half, and the monolayer becomes more fluidic due to the presence of even very minute quantity (5%) of TCh. 相似文献
840.
Gupta A Mukherjee A Matsui K Roth JP 《Journal of the American Chemical Society》2008,130(34):11274-11275
Rice alpha-oxygenase (RalphaO) catalyzes the insertion of O2 into the Calpha-H bond of various fatty acids. The mechanism is thought to involve a tyrosyl radical as the oxidant on the basis of comparisons to the structurally homologous cyclooxygenase enzymes. Kinetic and spectroscopic results presented here for the wild-type RalphaO and the Tyr379Phe mutant indicate an irreversible H* abstraction mechanism and support the involvement of the proposed catalytic Tyr*. In addition, very large, weakly temperature dependent deuterium kinetic isotope effects (approximately 50) are observed, consistent with extensive nuclear tunneling. RalphaO, thus, presents a novel example where such quantum effects are associated with an amino acid radical-utilizing enzyme. 相似文献