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911.
El-Nahas AM Mangood AH Takeuchi H Taketsugu T 《The journal of physical chemistry. A》2011,115(13):2837-2846
The thermochemistry and kinetics of the pyrolysis of 2-butanol have been conducted using ab initio methods (CBS-QB3 and CCSD(T)) and density functional theory (DFT). The enthalpies of formation and bond dissociation energies of some alcohols including 2-butanol and its derived radicals have been calculated. A variety of simple and complex dissociations have been examined. The results indicated that dehydration to 1- and 2-butene through four-center transition states is the most dominant channel at low to moderate temperatures (T ≤ 700 K), where formation of butenes is kinetically and thermodynamically more favorable than other complex and simple bond scission reactions. Although the C-C bond fission channels require more energy than needed for some complex decomposition reactions, the former pathways predominate at higher temperatures (T ≥ 800 K) due to the higher values of the pre-exponential factors. The progress of the complex decomposition reactions has been followed through intrinsic reaction coordinate (IRC) calculations to understand the mechanism of transformation of 2-butanol to different products. 相似文献
912.
A time-dependent collisional-radiative model for air plasma has been developed to study the effects of nonequilibrium atomic
and molecular processes on population densities in a weakly ionized high enthalpy flow. This model consists of 15 species:
e-,N, N+,N2+,O, O+,O2+,O-,N2,N2+,NO, NO+,O2,O2+{{\rm e}^{-},{\rm N, N}^{+},{\rm N}^{2+},{\rm O, O}^{+},{\rm O}^{2+},{\rm O}^{-},{\rm N}_{2},{{\rm N}_{2}}^{+},{\rm NO, NO}^{+},{\rm O}_{2},{{\rm O}_{2}}^{+}}, and O2-{{{\rm O}_{2}}^{-}} with their major electronic excited states. Many elementary processes are considered in the number density range of 1012/cm3 ≤ N ≤ 1019/cm3 and the temperature range of 300 K ≤ T ≤ 40,000 K. We then compare our results with an existing collisional-radiative code to validate our model. Additionally,
the unsteady nature of pulsively heated air plasma is investigated. When the ionization relaxation time is of the same order
as the time scale of a heating pulse, the effects of unsteady ionization are important for estimating air plasma states. From
parametric computations, we determine the appropriate conditions for the collisional-radiative steady state, local thermodynamic
equilibrium, and corona equilibrium models in that density and temperature range. 相似文献
913.
Total synthesis of (+)-papulacandin D 总被引:1,自引:0,他引:1
A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. 相似文献
914.
Shigenobu Nishiguchi Akihiro Taguchi Tetsuya Kajimoto Yuri Yamazaki Yoshiaki Kiso 《Tetrahedron》2010,66(1):314-227
(+)-Negamycin was prepared in 13 steps in an overall yield of 31% from commercially available ethyl (R)-(+)-4-chloro-3-hydroxybutanoate. The key step in the reaction sequence was a highly stereoselective asymmetric Michael addition of chiral amine (−)-21 [(1S,2R)-(−)-2-methoxybornyl-10-benzylamine] into the α,β-unsaturated carbonyl moiety of key intermediate 8, thus establishing the second chiral center in (+)-negamycin. 5-epi-Negamycin was also prepared in a similar fashion. 相似文献
915.
Takuya Nakanishi Tsubasa Ueno Mariko Matsunaga Md. Zaved Hossain Khan Tetsuya Osaka 《Electroanalysis》2010,22(4):393-398
Potential response of indium tin oxide (ITO) electrode modified by treatment with disuccinimidyl suberate (DSS) was investigated to various target molecules. Distinctively, the DSS‐modified ITO electrode exhibited a potential shift to the molecules possessing an indole group such as tryptophan, tryptamine and indole propionic acid, while little response to benzoic acid, phenylalanine, proline, proline amide, and arginine was observed. In addition, the combination of this specificity to indoles and enantioselective affinity of human serum albumin (HSA), which was additionally immobilized on the DSS‐modified ITO electrode, brought about enantioselective potential response to tryptophan. 相似文献
916.
917.
Ueno Katsuhiro Hatada Naoyuki Han Donglin Toyoura Kazuaki Uda Tetsuya 《Journal of Solid State Electrochemistry》2020,24(7):1523-1538
Journal of Solid State Electrochemistry - Y-doped BaZrO3 (BZY) is a promising candidate for electrolytes in protonic ceramic fuel cells. To achieve the high proton conductivities of sintered... 相似文献
918.
919.
Consideration on formation mechanism of aromatic polyamide hollow spheres prepared by reaction‐Induced phase separation
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Hirofumi Nakayama Yuji Fujitsu Tetsuya Uchida Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2015,53(17):1966-1974
Hollow spheres of poly(1,4‐phenylene‐5‐hydroxyisophthalamide) had been obtained by the reaction‐induced phase separation during polymerization of 5‐hydroxyisophthalic acid and 1,4‐phenylene diamine in an aromatic solvent. In this study, formation mechanism of the hollow spheres was considered from the view points of eliminated small molecules, polymer structure, and cross‐linking reaction. With respect to the eliminated small molecules, water was the most desirable to form gas‐bubbles in droplets compared with methanol and acetic acid, due to the insolubility into the polymerization system. Rigid polymer structure was also needed to prepare hollow spheres owing to the rapid solidification of droplets. Further, phenolic hydroxyl group in 5‐hydroxy‐1,3‐phenylene moiety caused the ester‐amide exchange reaction to form cross‐linked skin layer in the droplets. The efficient formation of the skin layer was important to encapsulate gas‐bubbles in the droplets, resulting in the formation of hollow structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1966–1974 相似文献
920.