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141.
Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate. 相似文献
142.
Phase transitions and hysteresis in a cellular automata-based model of opinion formation 总被引:1,自引:0,他引:1
A particular case of a cellular automata-based model of two-state opinion formation in social groups with a strong leader is studied. We consider a 2D Euclidian geometry of social space and mutual interactions 1/r
n
. The model shows an interesting dynamics which can be analytically calculated. There are two stable states of the system: a cluster around the leader and unification. Unstable clusters may also appear. A variation in parameters such as the leader's strength or the social temperature can change the size of a cluster or, when they reach some critical values, make the system jump into another state. For a certain range of parameters the system exhibits bistability and hysteresis phenomena. We obtained explicit formulas for the cluster size, critical leader's strength, and critical social temperature. These analytical results are verified by computer simulations. 相似文献
143.
Using statistically designed experiments, 12,500 observations are generated from a 4-pieced Cobb-Douglas function exhibiting increasing and decreasing returns to scale in its different pieces. Performances of DEA and frontier regressions represented by COLS (Corrected Ordinary Least Squares) are compared at sample sizes ofn=50, 100, 150 and 200. Statistical consistency is exhibited, with performances improving as sample sizes increase. Both DEA and COLS generally give good results at all sample sizes. In evaluating efficiency, DEA generally shows superior performance, with BCC models being best (except at corner points), followed by the CCR model and then by COLS, with log-linear regressions performing better than their translog counterparts at almost all sample sizes. Because of the need to consider locally varying behavior, only the CCR and translog models are used for returns to scale, with CCR being the better performer. An additional set of 7,500 observations were generated under conditions that made it possible to compare efficiency evaluations in the presence of collinearity and with model misspecification in the form of added and omitted variables. Results were similar to the larger experiment: the BCC model is the best performer. However, COLS exhibited surprisingly good performances — which suggests that COLS may have previously unidentified robustness properties — while the CCR model is the poorest performer when one of the variables used to generate the observations is omitted. 相似文献
144.
Joe Zhu 《Annals of Operations Research》1996,66(5):311-335
This article employs new data envelopment analysis/assurance region (DEA/AR) methods to evaluate the efficiency of the 35 textile factories of the Nanjing Textiles Corporation (NTC), Nanjing, China. The returns to scale (RTS) of these factories were studied without assuming that the optimal DEA solutions were unique. All DMUs are identified with pointsE (Extreme Efficient),E (Efficient but not an extreme point) andF (Frontier but not efficient). We then further identify the nonfrontier DMUs with pointsNE, NE andNF according to whether they are projected onto a point inE, E, orF en route to evaluating their performances. All of the inefficient factories were in classNF and had unique optimal primal-dual solution pairs. Consequently, the solution pairs satisfy the strong complementary slackness condition (SCSC). Application of cone-ratio (CR) ARs reduced significantly the number of factories in classE, and showed that some AR-efficient factories were more flexible in adopting the mixture of central planning and market economies that China currently is trying to use. Also, linked-cone (LC) ARs were applied to measure maximum and minimum profit ratios. The SCSC multiplier space approach was utilized to analyze the sensitivity of the efficiency results to potential errors in the data with and without ARs. The results in this article suggest that collective units had a better performance than state-owned units in the two consecutive years analyzed.This paper was written while the author was at the School of Economics and Management, Southeast University, Nanjing 210018, P.R. China. 相似文献
145.
Contrary to the informations in the literature our results of equilibrium and kinetic measurements indicate that Al(III) and Pyridine-2,6-dicarboxylic Acid in the range ofpH=(3...5) only formed the complexes AlHL
2+ (log=7.44±0.2) and AlL
+ (log=11.37±0.06). 相似文献
146.
An electrostatic bond energy model is formulated to fit the enthalpies of formation and dipole moments of the alkanes and chloroalkanes. In this model, the charge distributions are calculated by an electrostatic approach similar to the "MSE" method, and the enthalpy of formation of a molecule is the sum of the bond energy terms plus the electrostatic energy of the interactions between the charges on all atoms. All parameters of this model are obtained by parameterization. The calculated dipole moments for 13 chloroalkanes and enthalpies of formation for 19 alkanes and non-geminal chloroalkanes agree with the determined values very well. To calculate the enthalpies of formation of geminal chloroalkanes, a correction mainly attributed to the van der Waals interactions in the geminal substituted group, about 24 kJ/mol per pair of geminal chlorine atoms, is introduced. 相似文献
147.
Jihong Cheng 《Journal of solid state chemistry》2004,177(1):126-133
LaGaO3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa1−yMgyO3−δ (LGM), La1−xSrxGa1−yMgyO3−δ (LSGM), and La1−xBaxGa1−yMgyO3−δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of VO·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling. 相似文献
148.
Maria?Victoria Roux Paul?J.?Smith Joel?F.?LiebmanEmail author 《Structural chemistry》2005,16(1):73-75
Despite their seeming simplicity, substituted guanidines have not particularly caught the attention of the thermochemical community. The current paper compares the enthalpy of formation of solid substituted guanidines with correspondingly substituted benzenes, also as solids. 相似文献
149.
Min Hsien Liu 《中国化学会会志》2007,54(1):141-148
Density functional theory (DFT) calculations are made and least squares calibration performed for various halohydrocabons, which were 27 straight‐chain alkyl halides, 20 branch‐chain alkyl halides and 19 aromatic halides, to determine their enthalpies of formation (ΔHf). The mean absolute error (M. |A.E.|) in ΔHf across 66 molecular computations was only 7.8 kJ/mol (1.9 kcal/mol). Grouping the molecules by their structural characteristics improved M. |A.E.| of ΔHf by 0.2–2.2 kJ/mol over that obtained using corresponding modified data for the same 66 unclassified molecules. 相似文献
150.
Lj.?Radonji 《Journal of Thermal Analysis and Calorimetry》2005,79(3):487-492
Summary The subject of this study was to investigate the effect of fluoride ions addition on the temperature of sol gel mullite formation based on the hypotheses that the presence of fluoride ions can decrease the temperature of mullite formation (in respect to common 980°C, in sol-gel processing). Polymeric sols were prepared by mixing TEOS and aluminum nitrate nanohydrate and by adding fluoride ions (from 2 to 5 mass%). DTA, TG, XRD and SEM were used for characterisation of mullite gel and crystalline mullite. The experimental results confirmed that the addition of fluoride ions decrease the temperature of mullite formation up to 890°C for the fluorine concentration of 3.5 mass%. Experimental results showed that the temperature of mullite formation is not a simple function of the fluoride ion content. The mechanism of fluorine effect was discussed in terms of the gelling process, gel structure and the phase separation before the mullite formation. 相似文献