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131.
A correlation between two noise processes driving the thermally activated particles in a symmetric triple-well potential may cause a symmetry breaking and a difference in relative stability of the two side wells with respect to the middle one. This leads to an asymmetric localization of population and splitting of Kramers' rate of escape from the middle well, ensuring a preferential distribution of the products in the course of a parallel reaction. 相似文献
132.
Tushar S. Basu Baul Wandondor Rynjah Claudio Pettinari Robert Jirásko Anthony Linden 《Journal of organometallic chemistry》2007,692(17):3625-3635
Reactions of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L1HH′: X = H; L2HH′: X=2′-OCH3; L3HH′: X = 3′-CH3; L4HH′: X = 4′-CH3; L5HH′:X = 4′-Cl) with nOct2SnO in 2:1 and 1:1 molar ratios have been investigated. Two types of complexes, nOct2Sn(LH)2 and {[nOct2Sn(LH)]2O}2, were isolated and they have been characterized by 1H, 13C, 119Sn NMR, ESI-MS, IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of nOct2Sn(L1H)2 (1), {[nOct2Sn(L2H)]2O}2 (3) and {[nOct2Sn(L3H)]2O}2(4) were determined. The mononuclear complex 1 was found to adopt a skew-trapezoidal bipyramidal arrangement around the tin atom while 3 and 4 are centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complexes containing a planar Sn4O2 core in which two μ3-oxo O-atoms connect an Sn2O2 ring to two exocyclic Sn-atoms. The solution structures were confirmed by 119Sn NMR spectroscopy by observing one tin resonance in compound 1 and two tin resonances in {[nOct2Sn(L5H)]2O}2 (5). {[nOct2Sn(L2H)]2O}2 (3) and {[nOct2Sn(L3H)]2O}2 (4) undergo very complex exchange processes in deuteriochloroform solution, which has been confirmed by variable temperature 1H NMR spectroscopy. The cleavage of the most labile bond in the molecule was studied by ESI mass spectrometry. 相似文献
133.
Tushar S. Basu Baul Cheerfulman Masharing Eleonora Rivarola Frank E. Smith Ray Butcher 《Structural chemistry》2007,18(2):231-235
Reactions of equimolar quantities of potassium 2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene]amino}acetate, with R n SnX4?n (R: benzyl– and n=2 or 3) in methanol yielded products of compositions LHSn(PhCH2)3 and LSn(PhCH2)2, respectively. The complexes were characterized by microanalysis, IR, NMR (1H, 13C, 119Sn) and 119mSn Mössbauer spectroscopy. A full characterization of the structure of the complex, tribenzyl{2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene]amino}acetato}tin(IV), was carried out by single crystal X-ray crystallography. The compound exists as centrosymmetric dimers in which two ligand molecules bridge the two tin centres. Each of the tin atoms in the dimeric unit is five coordinate in an approximately trigonal bipyramidal configuration, with carbon atoms in the equatorial positions and oxygen atoms arranged axially. 相似文献
134.
Studies on plant metabolites have gained renewed interest in recent years because these can serve as renewable chemicals for the development of a sustainable society. Among various plant secondary metabolites, terpenoids constitute the major component and triterpenoids are the 30C subset of it. In recent years, triterpenoids have drawn the attention of scientific community due to many of its potential and realized applications in medicine, drug delivery, thermochromic materials, pollutant capture, catalysis, liquid crystals, etc. In this personal review, we have discussed our computational results carried out on sixty representative naturally occurring triterpenoids demonstrating that all the triterpenoids are renewable functional nano‐entities. Study of the self‐assembly of several triterpenoids such as betulin, betulinic acid, oleanolic acid, glycyrrhetinic acid and arjunolic acid and their derivatives in different liquids have also been discussed. Moreover, the utilization of the resulting supramolecular architectures such as vesicles, spheres, flowers and fibrillar networks of nano‐ to micrometer dimensions and gels have also been discussed in the perspective of green, renewable and nanos. 相似文献
135.
We have studied the barrier crossing dynamics in presence of non-Gaussian noises. It has been observed that multiplicative colored non-Gaussian noise can induce resonant activation (RA). The conspicuous dependence of mean first passage time (MFPT) on correlation time (τ2) of additive colored noise having fixed variance have been analyzed. Beyond a critical value of τ2 the MFPT increases for a given rate of increase of noise strength with τ2 if the additive colored noise is non-Gaussian. The MFPT first decreases with increase of the non-Gaussian parameter (measures deviation from Gaussian character) of multiplicative colored noise followed by an increase exhibiting a minimum. The appearance of the minimum critically depends on the additive noise. 相似文献
136.
Sannigrahi A Arunbabu D Sankar RM Jana T 《The journal of physical chemistry. B》2007,111(42):12124-12132
In the present work, a series of novel random polybenzimidazole (PBI) copolymers consisting of m- and p-phenylene linkages are synthesized from various stoichiometric mixtures of isophthalic acid (IPA) and terephthalic acid (TPA) with 3,3',4,4'-tetraaminobiphenyl (TAB) by solution copolycondensation in polyphosphoric acid (PPA). The resulting copolymers are characterized by different techniques to obtain their molecular properties parameters. The monomer concentration in the polymerization plays an important role in controlling the molecular weight of the polymer. Surprisingly, a simple change in the dicarboxylic acid architecture from meta (IPA) to para (TPA) increases the molecular weight of the copolymers, which is maximum for the para homopolymer. The low solubility of TPA in PPA is found to be the dominating factor for obtaining the higher molecular weight polymer in the case of the para structure. FT-IR study shows that the introduction of the para structure enhances the conjugation along the polymer chain. The positive deviation of the copolymer composition from the feed ratio is due to the higher reactivity ratio of TPA than IPA, which is obtained from proton NMR studies. The incorporation of the para structure in the chain enhances the thermal stability of the polymers. The para homopolymer shows 59 degrees C lower glass transition temperature compare to the meta homopolymer indicating enhancement of the flexibility of the polymer chain due the introduction of the p-phenylene linkage in the backbone. The T(g) of the copolymers shows both positive and negative deviation from the expected T(g) calculated by the Fox equation. The enhanced conjugation of the polymer chains also influences the photophysical properties of the polymers in solution. All the PBI polymers exhibit strong fluorescence in dimethylacetamide solution. As expected, that all the polymers are amorphous in nature reveals that the copolymerization does not influence the packing characteristics of the PBI chains. 相似文献
137.
We report a class of 'wet' MEMS elastomer-metal electrostatic actuators which can actuate in air, oil or water environments with no external fluidic connections, has actuation voltages lower than 15 V and is compatible with widespread PDMS microfluidics. 相似文献
138.
A mannose-derived furanoid sugar amino acid (Maa) induced helical turns in peptides having repeat units of Maa(Bn(2))-Phe-Leu, which aggregated into head-to-tail duplexes in the longer oligomers. 相似文献
139.
140.
Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity. 相似文献