全文获取类型
收费全文 | 1883篇 |
免费 | 25篇 |
国内免费 | 6篇 |
专业分类
化学 | 1051篇 |
晶体学 | 13篇 |
力学 | 71篇 |
数学 | 111篇 |
物理学 | 316篇 |
无线电 | 352篇 |
出版年
2023年 | 10篇 |
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 26篇 |
2019年 | 21篇 |
2018年 | 15篇 |
2017年 | 22篇 |
2016年 | 43篇 |
2015年 | 39篇 |
2014年 | 84篇 |
2013年 | 96篇 |
2012年 | 192篇 |
2011年 | 147篇 |
2010年 | 132篇 |
2009年 | 130篇 |
2008年 | 133篇 |
2007年 | 95篇 |
2006年 | 85篇 |
2005年 | 89篇 |
2004年 | 70篇 |
2003年 | 67篇 |
2002年 | 14篇 |
2001年 | 11篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1997年 | 8篇 |
1996年 | 13篇 |
1995年 | 17篇 |
1994年 | 14篇 |
1993年 | 17篇 |
1992年 | 7篇 |
1991年 | 12篇 |
1990年 | 9篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1986年 | 7篇 |
1984年 | 17篇 |
1983年 | 9篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 13篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1975年 | 9篇 |
1974年 | 7篇 |
1963年 | 5篇 |
1961年 | 5篇 |
1936年 | 13篇 |
排序方式: 共有1914条查询结果,搜索用时 859 毫秒
61.
Sambhu Bhadra 《European Polymer Journal》2007,43(10):4332-4343
In situ synthesis of polyaniline (PAni) coated pyrogenic or fumed silica (PCFS) and precipitated silica (PCPS) were carried out by the oxidative polymerization of aniline in presence of fumed silica (FS) and precipitated silica (PS). Both uncoated and PAni coated silica fillers were characterized through scanning electron microscope (SEM), infrared spectroscopy and thermo-gravimetric analysis (TGA) to evaluate particle morphology and physico-chemical character of coated and uncoated silica particles. Semi-conducting composites made from two different types of PAni coated silica fillers with NBR exhibit different trend in the variation of electrical properties under different temperature and pressure. These differences in electrical properties of two types of composites are mainly due to physico-chemical characteristics of filler particles as well as their distribution in the polymer matrix. This type of composites may be used as semi-conducting and ESD (electrostatic discharge) material. 相似文献
62.
Nath M Jairath R Eng G Song X Kumar A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):3155-3161
New diorganotin(IV) derivatives of the general formula R2Sn(Umb)2 (where R = n-Bu, n-Oct and Ph; Umb = umbelliferone anion) have been synthesized either by the reaction of R2SnO with umbelliferone under azeotropic removal of water or by the reaction of R2SnCl2 with sodium salt of umbelliferone. Further, the adducts of the general formula R2Sn(Umb)2.phen (where R = n-Bu and n-Oct; phen = 1,10-phenanthroline) have also been synthesized by the interaction of R2Sn(Umb)2 with 1,10-phenanthroline. The bonding and coordination behavior in these derivatives are discussed on the basis of IR and 119Sn M?ssbauer spectroscopic studies in solid state. Their coordination behavior in solution is discussed by the multinuclear (1H, 13C and 119Sn) NMR spectral studies. The M?ssbauer and IR studies indicate that umbelliferone acts as a monoanionic bidentate ligand in R2Sn(Umb)2 coordinating through O(7) and O(1). A distorted octahedral geometry around tin has been proposed for R2Sn(Umb)2 as well as for R2Sn(Umb)2.phen in solid state. The newly synthesized derivatives have been tested for their anti-inflammatory and cardiovascular activities. The average LD50 value >1000 mg kg(-1) of these compounds indicates their safety margin. 相似文献
63.
Summary The kinetics of oxidation of 2-methoxyethanol and 2ethoxyethanol by vanadium (V) in aqueous sulphuric acid medium has been studied. The order of reaction with respect to the oxidant and substrate has been found to.be unity. The energy of activation has also been calculated graphically. A probable mechanism has been proposed. 相似文献
64.
The stepwise acid dissociation constants for p-benzohydroquinone (QH2) in aqueous media have been explicitly calculated for the first time, with the INDO parametrized SCF –MO method. We have optimized the geometries of QH2, QH?, and Q2? and of the QH2 · 6H2O, QH? · (H3O+) · 5H2O, and Q2? · (H3O+)2 · 4H2O systems that model the solvated species. The presence of the associated water molecules (and hydronium ions) account for the stabilization due to hydrogen bonding as well as for a part of the effect of interaction of these molecules with the respective reaction fields in an aqueous medium. To simulate the first solvation shell in a more complete manner, four more water molecules have been considered to be placed above and below the quinonoid ring and the optimized geometries of the resulting hydrated species, QH2 · 10H2O, QH? · (H3O+) · 9H2O, and QH? · (H3O+) · 8H2O, have been determined. The standard free-energy changes calculated for the dissociation of QH2 into QH? and H+ is 0.0251 Hartree (65.9 kJ mol?1) and that of QH? into Q2? and H+ is 0.0285 Hartree (74.8 kJ mol?1). Experimentally observed dissociation constants for these two steps correspond to free-energy changes of 0.0214 Hartree (56.2 kJ mol?1) and 0.0248 Hartree (65.1 kJ mol?1), respectively. © 1995 John Wiley & Sons, Inc. 相似文献
65.
Sadasivam Senthilkumar Sukhendu Nath Haridas Pal 《Photochemistry and photobiology》2004,80(1):104-111
Experimental results on various photophysical properties of coumarin‐30 (C30) dye, namely, Stokes' shift (Δv), fluorescence quantum yield (τf), fluorescence lifetime (τf), radiative rate constant (kf) and nonradiative rate constant (knr), as obtained using absorption and fluorescence measurements have been reported. Though in most of the solvents the properties of C30 show more or less linear correlation with the solvent polarity function, Δf= [(ε ‐ 1)/(2ε+ 1) ‐ (n2 ‐ 1)/ (2n2+ l)], they show unusual deviations in nonpolar solvents at one end and in high‐polarity protic solvents at the other end. From the solvent polarity and temperature effect on the photophysical properties of the dye, following inferences have been drawn: ( 1 ) in nonpolar solvents, the dye exists in a nonpolar structure, where its 7‐NEt2 substituent adopts a pyramidal configuration and the amino lone pair is out of resonance with the benzopyrone π cloud; ( 2 ) in medium to higher polarity solvents, the dye exists in a polar intra‐molecular charge transfer structure, where the 7‐NEt2 group and the 1,2‐benzopyrone moiety are in the same plane and the amino lone pair is in resonance with the benzopyrone π cloud; ( 3 ) in protic solvents, the dye‐solvent intermolecular hydrogen bonding influences the photophysical properties of the dye; and ( 4 ) in high‐polarity protic solvents, the excited C30 undergoes a new activation‐controlled nonradiative deexcitation process because of the involvement of a twisted intra‐molecular charge transfer (TICT) state. Contrary to most other TICT molecules, the activation barrier for this deexcitation process in C30 is observed to increase with solvent polarity. A rational for this unusual behavior has been given on the basis of the solvent polarity‐dependent stabilization and crossing of relevant electronic states and the relative propensity of interconversion among these states. 相似文献
66.
67.
Praharaj S Ghosh SK Nath S Kundu S Panigrahi S Basu S Pal T 《The journal of physical chemistry. B》2005,109(27):13166-13174
Gold nanoparticles of variable sizes have been synthesized in toluene employing two-phase (water-toluene) extraction of AuCl4- followed by its reduction with sodium borohydride in the presence of a series of cationic surfactants of a homologous series having the general formula C(n)TAC. The solubility features of the gold particles in the organic solvent have been accounted qualitatively by calculating the van der Waals interaction potential between the particles. The effect of thermal energy and medium dielectric constant on the stability of metal particles has been studied by measuring the surface plasmon resonance. The stabilization of surfactant-mediated gold particles as hydrosol or organosol has been elucidated by considering the double-layer interaction as a function of the dielectric constant of the solvent medium. The influence of the counterion of the phase transfer reagent and stabilizing ligand on the photochemical stability of the gold colloids has been investigated. The fluorescence probe 1-methylaminopyrene (MAP) was considered for the surface functionalization of the gold particles, and it has been found that there is an enhancement of molecular fluorescence from the gold-probe assembly. 相似文献
68.
Our own work on steroid compounds with defined conformation as chiral model compounds for investigations of chemo-, regio- and stereoselectivity of metal-mediated new reactions is reviewed. Reactions with nickelacycles, (π-allyl)zirconoxycarbene complexes, iron tricarbonyl complexes of dienes and 1-azadienes, the Ru-catalyzed synthesis of 1,3-dihydropyrrol-2-ones from 1-azadienes, the Pd-catalyzed cyclopropanation of 1-azadienes, syntheses with cuprio steroids, copper complexes of amino alcohol derivatives and the copper-mediated hydroxylation of nonactivated C-H bonds with molecular oxygen are discussed. 相似文献
69.
Submerged culture fermentation studies were carried out in batch mode for optimizing the environmental parameters and carbon
source requirement by Pseudomonas elodea for the production of gellan gum. The maximum production of gellan gum was obtained with 16-h-old culture and 8% inoculum
at 30°C and pH 7.0 after 52 h of incubation (6.0 g/L). Of the various carbon sources tested, 2% sucrose, glucose, and soluble
starch yielded considerably high amounts of gellan. Studies on the concentration of various carbohydrates on gellan gum production
indicated that the optimum concentration of glucose and starch was 3%, whereas for sucrose it was 4%. The addition of glucose
in the medium above 3% had a detrimental effect on gellan yield. The investigation of intermediate two-step addition of glucose
under identical conditions of fermentation showed an enhanced production of gellan (8.12 g/L) as compared with the control
(6.0 g/L). To optimize the recovery of gellan from fermented broth, different solvents were tested for precipitation of gellan
gum. Among the various solvents tested, tetrahydrofuran gave better recovery of gellan (82%) as compared with the conventional
solvent isopropanol (49%). 相似文献
70.
The viscosity deviation (Δη), the excess molar volume (V
E) and the ultrasonic speed (u) have been investigated from viscosity (η) and density (ρ ) measurements of binary liquid mixtures of 1,2-dimethyoxyethane with methanol, ethanol, propan-1-ol, butan-1-ol,
pentan-1-ol, hexan-1-ol or octan-1-ol over the entire range of composition at 298.15 K. The excess volumes are negative over
the entire range of composition for all of the mixtures with the exception of hexan-1-ol and octan-1-ol. The excess isentropic
compressibilities (K
S
E) and viscosity deviations are negative for all of the mixtures. The magnitudes of the negative values of V
E decrease with the number of carbon atoms of the alkan-1-ol. The trend of increasing K
S
E values with the chain length of the alkanol is similar to that observed in the case of V
E. Graphs of V
E, Δ η, K
S
E, Δ u, L
f
E and Z
E against composition are presented as a basis for a qualitative discussion of the results. 相似文献