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131.
CCl2(A1B1)被O2及取代甲烷类分子猝灭的动力学研究 总被引:2,自引:0,他引:2
对CCl4/Ar混合气体放电产生CCl2自由基,再用541.52nm激光将电子基态CCl2激发到激发态A^1B1(0,4,0)振动态k=0能级上,通过检测 激发态CCl2时间分辨荧光信号,测得室温下CCl2(A^1B1)被O2,CF4,CF2Cl,CH3NO2,CH2Br2等分子猝灭的实验结果,用改进的三能级模型分析处理实验数据,获得态分辨速常数KA和Ka值,并对实验结果进行了讨论。 相似文献
132.
František Kopecký Božena Kopecká Pavol Kaclík 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(3-4):215-217
The solubility of nimodipine was measured in aqueous solutions of the following cyclodextrins: -cyclodextrin (-CD), hydroxypropyl--CD (HP--CD), -cyclodextrin (-CD), random substituted methyl--CD (M--CD), three hydroxypropyl--CDs (HP--CD) with mutually different average degree of substitution, and hydroxypropyl--cyclodextrin (HP--CD). From the determined linear solubility diagrams the values of the binding constant K11 of the inclusion complexes of nimodipine with the respective CDs were evaluated. The -CDs efficiently solubilized sparingly soluble nimodipine, the highest value of K11 was found for M--CD (1680 M-1), followed by -CD (550 M-1) and HP--CDs, where the higher degree of substitution lowered K11. Only slight solubilization of nimodipine was observed in the solutions of the -CDs and HP--CD. 相似文献
133.
我们用Fe_2(SO_4)_3·xH_2O为催化剂,对2-甲基-2-已醇脱水生成烯烃反应的溶剂化能力及其动力学做了研究,测定了20种不同溶剂中的反应速率常数和以丙至辛6种直链醇为溶剂于不同温度下反应的速率常数,确定了溶剂化能力与溶剂介电常数之间的线性关系。这方面工作尚未见报道。 相似文献
134.
Titanosilicates with complete or partial substitution of Ge or Nb in the framework and having the mineral pharmacosiderite topology were hydrothermally prepared and their ion-exchange properties towards Cs were studied for Ti/Ge/Si, Ti/Si, Nb/Ti/Si and pure Ge phases. The basis for the differences in the ion exchange properties measured as distribution coefficients (Kd) for these materials are detailed via structural characterization using the Rietveld refinement technique on the X-ray powder diffraction data. The differences in affinity towards Cs+ result either from the degree of hydration of the exchanger resulting in different coordination environments or the position of cesium ion in the eight-ring channel. 相似文献
135.
136.
Liliana N. Trevani Jenene C. Roberts Peter R. Tremaine 《Journal of solution chemistry》2001,30(7):585-622
The spectra of copper(II)–ammonia solutions in 2 mol-kg–1 NH4NO3(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH3)n
2+, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH4NO3(aq). The formation constants of Cu(NH3)n
2+ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg–1 CF3SO3H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH3)4
2+ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu2+ and the Cu(NH3)n
2+ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes. 相似文献
137.
Zeisler R 《Analytical and bioanalytical chemistry》2004,378(5):1277-1283
NIST maintains a portfolio of more than 1300 standard reference materials (SRM), more than a third of these relating to measurements in the biological and environmental fields. As part of the continuous renewal and replacement efforts, a set of new marine sediments has been recently developed covering organic and inorganic determinations. This paper describes the steps taken in sample preparation, homogeneity assay, and analytical characterization and certification with specific emphasis on SRM 2702 inorganics in marine sediment. Neutron activation analysis showed the SRM to be highly homogeneous, opening the possibility for use with solid sampling techniques. The certificate provides certified mass fraction values for 25 elements, reference values for eight elements, and information values for 11 elements, covering most of the priority pollutants with small uncertainties of only several percent relative. The values were obtained by combining results from different laboratories and techniques using a Bayesian statistical model. An intercomparison carried out in field laboratories with the material before certification illustrates a high commutability of this SRM.Electronic Supplementary Material Supplementary material is available in the online version of this article at 相似文献
138.
The cyclic voltammetric behaviour of Eu3+/Eu2+ couple at hanging mercury drop electrode (HMDE) has been studied in chloride, bromide, iodide, thiocyanate and EDTA supporting
electrolytes. The apparent rate constant and transfer coefficient for these systems have been calculated at various voltage
scan rates, without using the data for standard or formal potential. The values have been compared with those obtained by
earlier workers through other electrochemical methods. 相似文献
139.
A stochastic (Monte Carlo) simulation is used to investigate thermodynamic and kinetic contributions from the reversible A <--> B reaction in capillary electrophoresis (CE). The effects of equilibrium constant, rate constant, and electrophoretic mobility on the molecular zone profiles and the corresponding statistical moments are evaluated. As the reaction approaches steady state, the velocity of the zone is governed by the equilibrium constant and the electrophoretic mobilities of the reacting molecules. When the equilibrium constant is less than unity, the mean zone velocity is more similar to that of the reactant A. Conversely, when the equilibrium constant is greater than unity, the velocity is more similar to that of the product B. The extent of zone-broadening and asymmetry at steady state is dependent upon the equilibrium constant, the characteristic reaction lifetime, and the electrophoretic mobility difference between reacting molecules. If all other parameters are held constant, the plate height is greatest and skew is least when the equilibrium constant is unity. The plate height increases linearly with the characteristic reaction lifetime and electrophoretic mobility difference, whereas the skew is independent of these parameters. These conclusions have important implications for the elucidation of thermodynamic and kinetic information from experimental data. 相似文献
140.
Dachun Yao 《Analytica chimica acta》2003,478(1):23-30
A new detection system based on microdialysis sampling and chemiluminescence (CL) reaction was developed for in vivo monitoring of uric acid (UA) with high sensitivity, selectivity and accuracy. The uric acid is indirectly monitored by CL detection of enzymatic reaction product formation (H2O2), catalyzed by Uricase. A microprobe was modified and coated with immobilized enzyme through a Streptavidin-biotin mediated linker by using a chitosan support membrane, polyurethane trapped ferrocene film is employed to protect the probe surface and diminish the interference from reductant molecules, which often are present in the blood (e.g. ascorbic acid). The earlier mentioned probe and the constructed sensor can detect uric acid in the range of 0.01-1 mM with detection limit (3σ) of 5 μM. Finally, the system is used to monitor uric acid (UA) variation through an acute myocardial infarction (AMI) model. Following AMI-induced oxidative stress, the UA level decreases continuously, thus suggesting that UA plays a protective role as a substitute antioxidant. Furthermore, the in vivo monitoring results show good agreement with those obtained by a standard method, and the procedure is recommended for in vivo and real time monitoring of UA. In addition, the proposed method can be more accurate since the UA may be potentially oxidized by in vitro exposure to oxygen in the presence of a catalyst. 相似文献