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991.
Choudhary TV Malandra J Green J Parrott S Johnson B 《Angewandte Chemie (International ed. in English)》2006,45(20):3299-3303
992.
M. Jiménez-Reyes M. Solache-Ríos A. Rojas-Hernández 《Journal of solution chemistry》2006,35(2):201-214
The specific ion interaction theory (SIT) was applied to the first hydrolysis constants of Eu(III) and solubility product
of Eu(OH)3 in aqueous 2, 3 and 4 mol⋅dm−3 NaClO4 at 303.0 K, under CO2-free conditions. Diagrams of pEuaq versus pCH were constructed from solubilities obtained by a radiometric method, the solubility product log10 Ksp, Eu(OH)3I {Eu(OH)3(s)
Euaq3++ 3OHaq− } values were calculated from these diagrams and the results obtained are log10 Ksp,Eu(OH)3I = − 22.65 ± 0.29, −23.32 ± 0.33 and −23.70 ± 0.35 for ionic strengths of 2, 3 and 4 mol⋅dm−3 NaClO4, respectively. First hydrolysis constants {Euaq3++H2O
Eu(OH)(aq)2++H+ } were also determined in these media by pH titration and the values found are log10βEu,HI = − 8.19 ± 0.15, −7.90 ± 0.7 and −7.61 ± 0.01 for ionic strengths of 2, 3, and 4 mol⋅dm−3 NaClO4, respectively. Total solubilities were estimated taking into account the formation of both Eu3+ and Eu(OH)2+ (7.7 < pCH < 9) and the values found are: 1.4 × 10−6 mol⋅dm−3, 1.2 × 10−6 mol⋅dm−3 and 1.3 × 10−6 mol⋅dm−3, for ionic strengths of 2, 3 and 4 mol⋅dm−3 NaClO4, respectively. The limiting values at zero ionic strength were extrapolated by means of the SIT from the experimental results
of the present research together with some other published values. The results obtained are log10 Ksp, Eu(OH)3o = − 23.94 ± 0.51 (1.96 SD) and log10βEu,H0 = − 7.49 ± 0.15 (1.96 SD). 相似文献
993.
A study was carried out to compare the binding affinities of 1-dodecanethiol and dodecylamine for small Pt nanoparticles. The results showed that the affinity of thiol for Pt nanoparticles increases with increasing particle size whereas the affinity of amine for Pt nanoparticles decreases. The divergence in binding affinities has resulted in differences in catalytic activities of thiol- and amine-protected Pt nanoparticles in the room temperature electro-oxidation of methanol (a fuel cell reaction). It was therefore possible for the larger Pt nanoparticles to be catalytically more active than the smaller Pt nanoparticles up to a certain critical size, before the surface area effects of nanoparticles become noticeable. 相似文献
994.
Hayman CM Larsen DS Simpson J Bailey KB Gill GS 《Organic & biomolecular chemistry》2006,4(14):2794-2800
A short synthesis of 6,6,6-trifluoro-L-acosamine 15 and 6,6,6-trifluoro-L-daunosamine 19 has been accomplished. The pyranose ring system of these carbohydrate analogues was formed by a hetero-Diels-Alder reaction of vinylogous imide 11 and ethyl vinyl ether which gave adduct 12a in 40% yield. Hydroboration gave 13 and subsequent hydrogenolytic removal of the (R)-2-phenylethyl chiral auxiliary gave ethyl 6,6,6-trifluoro-L-acosaminide 14. Acid hydrolysis furnished target 15. Glycoside 13 was N-trifluoroacetylated to give 16, the structure was confirmed by single crystal X-ray diffraction. The C-4 stereochemistry of 16 was inverted by Swern oxidation of the 4-OH group, and subsequent borohydride reduction to give 17. Hydrogenolytic removal of the auxiliary gave ethyl-6,6,6-trifluoro-L-daunosaminide 18. Acid hydrolysis provided 19. 相似文献
995.
Nozal Nalda MJ Bernal Yagüe JL Gómez MT Jiménez Sevilla JJ Bernal del Nozal J Higes Pascual M 《Journal of separation science》2006,29(3):405-413
A new LC-ESI-MS method was developed for the determination of residues of the antibacterial tylosins A, B, C and D in honey. The procedure employed an SPE on polymeric cartridges for the isolation of tylosins from diluted honey. Chromatographic separation of the tylosins was performed on a C18 column (150 x 4.60 mm2 ID, 5 microm) using a ternary gradient made of formic acid 1% in water (solvent A), methanol (solvent B) and ACN (solvent C) as mobile phase, at 30 degrees C and at a flow rate of 0.8 mL/min. Average analyte recoveries for the studied compounds ranged from 89 to 106% in replica sets of fortified honey samples. The detection limits for the four drugs studied were between 2 and 3 microg/kg. The developed method has been applied to the analysis of tylosin residues in honey from veterinarian treated beehives fed with the technical product, which contains the four compounds and is a new candidate antibiotic to treat American foulbrood disease of honey bee colonies. 相似文献
996.
A miniaturized pulsed discharge detector (Mini-PDD) has been successfully demonstrated for comprehensive 2-D GC (GC x GC) analysis of pyrolysis gasoline and the pyrolysis GC x GC analysis of a polyethylene copolymer. The detector cell volume of the Mini-PDD is reduced to 25% of the Valco plug-in PDD D-3. An n-C11 peak width at base is 96 ms for the Mini-PDD, about 23% larger than a peak width of 78 ms detected by a flame ionization detector (FID). The Mini-PDD has sufficient response time for most GC x GC applications. When Mini-PDD is operated in helium photoionization mode (Mini He-PDD), it is a universal detector for both inorganic and organic compounds. This is especially useful when detection of water is needed in GC x GC applications. When krypton is doped in the helium discharge gas (Mini Kr-PDD), it can suppress signals of compounds having higher ionization potentials and enhance relative signal intensities of aromatic compounds. The determination of aliphatic to aromatic hydrocarbon ratios is essential to the operation of petroleum crackers. Comparison of the signal from two modes of the Mini-PDD is a simple and fast way to verify the location of aromatics in comprehensive 2-D gas chromatograms. 相似文献
997.
Jiménez Blanco JL Bootello P Benito JM Mellet CO García Fernandez JM 《The Journal of organic chemistry》2006,71(14):5136-5143
Beta-(1-->6)-linked pseudodi- and pseudotrisaccharides incorporating alternating pseudoamide-type (urea, thiourea, guanidine) intersaccharide bridges have been prepared and evaluated as phosphate binders in water. The monosaccharide subunits induce the Z,Z rotameric form at the pseudoamide segments, thus favoring their participation in bidentate hydrogen-bond interactions with oxoanions. Moreover, the conformational properties about the anomeric C-1-N bonds and the sugar C-5--C-6 bonds privilege orientations that facilitate both the desolvation of the incoming anionic guest and the stabilization of the complex by cooperative interactions. Measurable association constants (K(as)) toward dimethyl and, especially, phenyl phosphate were obtained from NMR titration experiments for both series of glucooligomers, the binding affinity being strongly dependent on the nature of the pseudoamide functionality. Guanidinium derivatives, for which charge neutralization was expected to contribute to phosphate binding, were superior to the neutral thiourea and urea derivatives (K(as) = 48-60 M(-1) for 1:1 complexes with phenyl phosphate dianion). Interestingly, the thiourea oligomers exhibited association constants of the same order of magnitude (K(as) = 25-40 M(-1)), much higher than those observed for the urea analogues (K(as) = 2-3 M(-1)), which is ascribed to a less efficient solvation of the thiocarbonyl derivatives. 相似文献
998.
A method to facilitate regioselective formation of multiple dicarba isosteres of cystine is described. A sequence of ruthenium-catalyzed cross metathesis and rhodium-catalyzed hydrogenation of nonproteinaceous allylglycine derivatives has been developed to achieve high-yielding and unambiguous formation of diaminosuberic acid derivatives. Allylglycine derivatives readily undergo ruthenium-catalyzed metathesis and hydrogenation to yield diaminosuberic acid derivatives in near quantitative yield. Under the same experimental conditions, prenylglycine was found to be inert to both Grubbs' and Wilkinson's catalyzed metathesis and hydrogenation, respectively, but was readily activated for metathesis via cross metathesis with Z-butene. Subsequent cross metathesis of the metathesis-formed crotylglycine derivative, followed by hydrogenation, yielded the second diaminosuberic acid derivative in excellent yield. 相似文献
999.
Roux MV Temprado M Jiménez P Foces-Foces C Notario R Verevkin SP Liebman JF 《The journal of physical chemistry. A》2006,110(45):12477-12483
The enthalpies of combustion and sublimation of 2,5-thiophenedicarboxylic acid [CASRN 4282-31-9] were measured by rotary-bomb combustion calorimetry and the method of transference in a saturated stream of nitrogen, and the gas-phase enthalpy of formation was determined, Delta(f)H(o)(m)(g) = -(632.6 +/- 2.2) kJ x mol(-1). Standard ab initio molecular orbital calculations at the G2(MP2) and G3(MP2) levels were performed, and a theoretical study on the molecular and electronic structure of the compound has been carried out. The three most stable conformers have been explicitly taken into account. The calculated enthalpy of formation averaged using three different isodesmic reactions, -631.1 kJ x mol(-1), is in very good agreement with the experimental value. A comparison of the substituent effect of the carboxylic groups in benzene and thiophene ring has been made. The relative stability obtained for the substitution of two H atoms by COOH in position 2,5- for thiophene and 1,4- for benzene involve the same energetic effects, DeltaDelta(f)H(o)(m)= -747.6 +/- 2.4 and -748.2 +/- 2.7 kJ x mol(-1), respectively. 相似文献
1000.
Rubio N Sanchez-García D Jiménez-Banzo A Rey O Borrell JI Teixidó J Nonell S 《The journal of physical chemistry. A》2006,110(10):3480-3487
The need for new photodynamic-therapy photosensitizers has stimulated the search of new families of compounds absorbing strongly in the 700-900 nm range, the region where tissue is most transparent to radiation capable to induce the photodynamic effect. Using computational chemistry techniques, 3,6,13,16-tetraazaporphycenes were previously identified as interesting target candidates. This work reports on the photophysical and electrochemical properties of selected members of this new family of macrocycles. Compared to porphycenes, the tetra-aza counterparts show stronger absorption in the near-infrared, lower-lying singlet and triplet excited states, and substantially larger internal conversion quantum yield (Phi(IC) = 0.93). Energy transfer to oxygen is observed, which results in the formation of the cytotoxic species singlet oxygen. The process is found to be reversible, consistent with a triplet-energy value close to that of singlet oxygen. 相似文献