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991.
The activation energy of the enzyme-catalyzed reaction for uric acid decreases markedly in the presence of o-phenanthroline, which activates the bioelectrochemicla activity of the polypyrrole uricase electrode. The response current of the enzyme electrodeis independent of the concentration of o-phenanthroline. Based on the experimental results, the mechamsm of the enzyme-catalyzed reaction for uric acid in the presence of o-phenanthroline is presented as follows: E+A→EA, EA+S EAS, EAS→EA+P, where E, A, S and P are the enzyme, activator, substrate and product, respectively. The effects of pH value, potential and the uric acid concentration on the response currents of the uricase electrode have been studied in the presence of o-phenanthroline. In the presence of o-phenanthroline, the response current of the enzyme electrode increase linearly with increasing concentration of uric acid in the region of 0.07 to 0.67 mmol·L~(-1), therefore the polypyrrole uricase electrode which has once lost its activity can be activated and used again to determine the substrate concentration. 相似文献
992.
Núñez Lisardo Fraga L. Núñez M. R. Villanueva M. Rial B. 《Journal of Thermal Analysis and Calorimetry》2002,70(1):9-17
Curing reactions of the epoxy system consisting of a diglycidyl ether of bisphenol A (BADGE n=0) and m-xylylenediamine (m-XDA) were studied to calculate time-temperature-transformation (TTT) isothermal cure diagram for this system. Gel times were
measured as a function of temperature using solubility test. Differential scanning calorimetry (DSC) was used to calculate
the vitrification times. DSC data show a one-to-one relationship between T
g and fractional conversion, a independent of cure temperature. As a consequence, T
g can be used as a measure of conversion. The activation energy for the polymerization overall reaction was calculated from
the gel times obtained using the solubility test (41.5 kJ mol-1). This value is similar to the results obtained for other similar epoxy systems. Isoconversion contours were calculated by
numerical integration of the best fitting kinetic model.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
993.
M. T. Clavaguera-Mora S. Suriñach M. D. Baró S. Bordas N. Clavaguera 《Journal of Thermal Analysis and Calorimetry》1991,37(6):1261-1268
It is shown that the study of the kinetics of crystallization of an amorphous alloy may be used to obtain the correct form of the low temperature part of the time-temperature-transformation (T-T-T) curves. A unified review of the current kinetics of crystallization studies is presented and the general kinetic equation which gives the reaction rate as a function of temperature and crystalline fraction is shown to contain information related to theT-T-T-curves. Finally examples of application to two metallic glasses, Nd3Fe77B20 and Fe67.5Co15Nb1.5B16, obtained by rapid solidification techniques are presented. The comparison between theory and experiment is satisfactory.
Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60th birthday
This work was supported by the Comision Interdepartamental de Cienca y Tecnologia, CICYT (project No. MAT88-0439) which are acknowledged. 相似文献
Zusammenfassung Es wird gezeigt, daß die Untersuchung der Kristallisationskinetik von amorphen Legierungen genutzt werden kann, die korrekte Form des Niedertemperaturbereiches der Zeit-Temperatur-Transformation (T-T-T) Kurven zu erhalten. Es wird ein einheitlicher Überblick über die jüngsten Untersuchungen von Kristallisationskinetiken gegeben und an der allgemeinen Gleichung der Reaktionsgeschwindigkeit als eine Funktion von Temperatur und Kristallanteil wird gezeigt, daß sie Informationen bezüglich der T-T-T-Kurven beinhaltet. Letztlich wird eine Anwendung an zwei, durch schnelles Erstarren gewonnenen metallischen Gläsern Nd3Fe77B20 und Fe67.5Co15Nb1.5B16 dargelegt. Zwischen Theorie und Praxis konnte eine ausreichende Übereinstimmung festgestellt werden.
Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60th birthday
This work was supported by the Comision Interdepartamental de Cienca y Tecnologia, CICYT (project No. MAT88-0439) which are acknowledged. 相似文献
994.
Ramiro Pino Olivier Bokanowski Eduardo V. Ludeña Roberto López Boada 《Theoretical chemistry accounts》2007,118(3):557-561
Bearing in mind the insight into the Hohenberg–Kohn theorem for Coulomb systems provided recently by Kryachko (Int J Quantum
Chem 103:818, 2005), we present a re-statement of this theorem through an elaboration on Lieb’s proof as well as an extension
of this theorem to finite subspaces.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
995.
996.
Carolina A. Pinto P. M. Büchler J. Dweck 《Journal of Thermal Analysis and Calorimetry》2007,87(3):715-720
The catalyst
used in fluidized catalytic cracking (FCC) units of refineries after several
recovery cycles in regeneration units, reduces its activity and it is partially
substituted by new catalyst in the process. As it has a high silicon and aluminum
oxides content, the pozzolanic properties of a Brazilian FCC spent residual
catalyst, used in different substitution degrees to cement, were evaluated
by three thermal analysis techniques during the early stages of hydration
of a type II Portland cement. NCDTA curves show in real time that the residual
catalyst, accelerates the stages of cement hydration. TG and DSC curves of
respective pastes after 24 h of hydration evidence the pozzolanic activity
of the waste, respectively, by the lower water mass loss during the dehydroxylation
of the residual calcium hydroxide and by the lower dehydroxylation endothermal
effect. Within the analyzed period, the higher is the cement substitution
degree, the higher is the pozzolanic activity of the residual catalyst. 相似文献
997.
Changlun Chen Di Xu Xiaoli Tan Xiangke Wang 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):227-233
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions.
The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In
this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations
on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed
that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition
orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated
that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly
positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO−)
x
Co2−x
. Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA. 相似文献
998.
Cabeza A Ouyang X Sharma CV Aranda MA Bruque S Clearfield A 《Inorganic chemistry》2002,41(9):2325-2333
Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation. 相似文献
999.
Hernández de la Peña L Gulam Razul MS Kusalik PG 《The Journal of chemical physics》2005,123(14):144506
Quantum and classical simulations are carried out on ice Ih over a range of temperatures utilizing the TIP4P water model. The rigid-body centroid molecular dynamics method employed allows for the investigation of equilibrium and dynamical properties of the quantum system. The impact of quantization on the local structure, as measured by the radial and spatial distribution functions, as well as the energy is presented. The effects of quantization on the lattice vibrations, associated with the molecular translations and librations, are also reported. Comparison of quantum and classical simulation results indicates that shifts in the average potential energy are equivalent to rising the temperature about 80 K and are therefore non-negligible. The energy shifts due to quantization and the quantum mechanical uncertainties observed in ice are smaller than the values previously reported for liquid water. Additionally, we carry out a comparative study of melting in our classical and quantum simulations and show that there are significant differences between classical and quantum ice. 相似文献
1000.
Rodríguez A Muñoz M del Mar Graciani M Fernández Chacón S Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):9945-9952
The spontaneous hydrolysis of phenyl chloroformate was studied in water-ethylene glycol, EG, cationic, zwitterionic, nonionic, and anionic micellar solutions, the surfactants being tetradecyltrimethylammonium bromide, tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, tricosaoxyethylene glycol ether, and sodium dodecyl sulfate. The dependence of the observed rate constant on surfactant concentration as well as on the percentage by weight of EG, varying from 0 to 50 wt %, was investigated. Information about changes in the critical micelle concentrations, in the micellar ionization degrees (for ionic surfactants), in the aggregation numbers, and in the polarity of the interfacial region of the micelles upon changing the weight percent of EG was obtained through conductivity, surface tension, spectroscopic, and fluorescence measurements. A simple pseudophase model was adequate to rationalize the kinetic data. Micellar medium effects were explained by considering charge-charge interactions and polarity, ionic strength, and water content in the micellar interfacial region. The acceleration of the reaction produced by an increase in the amount of EG present in the mixture was explained on the basis of the substantial decrease in the equilibrium binding constant of phenyl chloroformate molecules to the micelles, resulting in the contribution of the reaction taking place in the bulk water-EG phase being more important. The weight percent of EG did not substantially influence the rate constant in the micellar pseudophase. 相似文献