全文获取类型
收费全文 | 1073篇 |
免费 | 34篇 |
国内免费 | 13篇 |
专业分类
化学 | 774篇 |
晶体学 | 5篇 |
力学 | 33篇 |
数学 | 110篇 |
物理学 | 198篇 |
出版年
2024年 | 4篇 |
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 44篇 |
2020年 | 21篇 |
2019年 | 27篇 |
2018年 | 38篇 |
2017年 | 28篇 |
2016年 | 36篇 |
2015年 | 29篇 |
2014年 | 37篇 |
2013年 | 90篇 |
2012年 | 63篇 |
2011年 | 61篇 |
2010年 | 55篇 |
2009年 | 58篇 |
2008年 | 57篇 |
2007年 | 67篇 |
2006年 | 50篇 |
2005年 | 48篇 |
2004年 | 58篇 |
2003年 | 33篇 |
2002年 | 42篇 |
2001年 | 11篇 |
2000年 | 10篇 |
1999年 | 13篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 10篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1962年 | 2篇 |
排序方式: 共有1120条查询结果,搜索用时 218 毫秒
101.
Park J Lang K Abboud KA Hong S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(7):2236-2245
A series of novel bis-urea-functionalized (salen)Co complexes has been developed. The complexes were designed to form self-assembled structures in solution through intermolecular urea-urea hydrogen-bonding interactions. These bis-urea (salen)Co catalysts resulted in rate acceleration (up to 13 times) in the hydrolytic kinetic resolution (HKR) of rac-epichlorohydrin in THF by facilitating cooperative activation, compared to the monomeric catalyst. In addition, one of the bis-urea (salen)Co(III) catalyst efficiently resolves various terminal epoxides even under solvent-free conditions by requiring much shorter reaction time at low catalyst loading (0.03-0.05 mol %). A series of kinetic/mechanistic studies demonstrated that the self-association of two (salen)Co units through urea-urea hydrogen bonds was responsible for the observed rate acceleration. The self-assembly study with the bis-urea (salen)Co by FTIR spectroscopy and with the corresponding (salen)Ni complex by (1)H NMR spectroscopy showed that intermolecular hydrogen-bonding interactions exist between the bis-urea scaffolds in THF. This result demonstrates that self-assembly approach by using non-covalent interactions can be an alternative and useful strategy toward the efficient HKR catalysis. 相似文献
102.
103.
Mohammed Belmekki Mouffak Benchohra Khalil Ezzinbi 《Applied Mathematics Letters》2011,24(11):1810-1816
In this paper, we establish sufficient conditions for the existence of solutions for some partial functional differential equations with state-dependent delay; we assume that the linear part is not necessarily densely defined and satisfies the well-known Hille–Yosida conditions. Our approach is based on a nonlinear alternative of Leray–Schauder type and integrated semigroup theory. An application is provided to a reaction–diffusion equation with state-dependent delay. 相似文献
104.
Lynch MS Cheng M Van Kuiken BE Khalil M 《Journal of the American Chemical Society》2011,133(14):5255-5262
We study photoinduced metal-nitrosyl linkage isomerism in sodium nitroprusside (Na(2)[Fe(II)(CN)(5)NO]·2H(2)O, SNP) dissolved in methanol using picosecond transient infrared (IR) spectroscopy. The high sensitivity of this technique allows the simultaneous observation of two known metastable (MS) iron-nitrosyl linkage isomers of SNP, [Fe(II)(CN)(5)(η(1)-ON)](2-) (MS1) and [Fe(II)(CN)(5)(η(2)-NO)](2-) (MS2), at room temperature. The transient population of free nitrosyl radicals (NO·) is also measured in the sample solution. These three transient species are detected using their distinct nitrosyl stretching frequencies at 1794 cm(-1) (MS1), 1652 cm(-1) (MS2), and 1851 cm(-1) (NO·). The metastable isomers and NO· are formed on a subpicosecond time scale and have lifetimes greater than 100 ns. A UV (400 nm)-pump power dependence study reveals that MS1 can be formed with one photon, while MS2 requires two photons to be populated at room temperature in solution. Other photodissociation products including cyanide ion, Prussian blue, and [Fe(III)(CN)(5)(CH(3)OH)](2-) are observed. We develop a photochemical kinetic scheme to model our data, and the analysis reveals that photoisomerization and photodissociation of the metal-NO moiety are competing photochemical pathways in SNP dissolved in methanol at room temperature. Based on the analysis, the solvent-associated Fe(III) species and Prussian blue form on a 130 and 320 ps time scale, respectively. The simultaneous detection and characterization of photoinduced linkage isomerism (MS1 and MS2) and photodissociation of the metal-NO bond in SNP highlights the importance of understanding the role played by metastable metal-nitrosyl linkage isomers in the photochemistry of metal-nitrosyl compounds in chemistry and biology. 相似文献
105.
In the present study, the density functional theory (DFT) and Gibbs free energy calculations were performed to investigate
the stability and tautomerism of C4-substituted-3,4-dihydropyrimidin-2(1H)-ones. Three different forms are possible for the ethyl 3,4-dihydropyrimidinones (ethyl 4-aryl-6-methyl-3,4-dihydropyrimidin-2(1H)-one-5-carboxylates, ethyl 4-aryl-2-hydroxy-6-methyl-1,4-dihydropyrimidine-5-carboxylates and ethyl 4-aryl-2-hydroxy-6-methyl-3,4-dihydropyrimidine-5-carboxylates)
forms that the most stable form is ethyl 4-aryl-6-methyl-3,4-dihydropyrimidin-2 (1H)-one-5-carboxylates (keto-form). The obtained data showed that the substitution on the C4-substitut position can be effective
on the equilibrium constant (K
eq). 相似文献
106.
In the presence of degenerate two-photon transitions the problem of the interaction between two two-level atoms and a single-mode is considered. Near resonance case, a closed form of the analytic solution for the wave function is obtained. The entanglement between an atom and field in the interacting system is studied by using the change in atomic and field entropies. The relationship between entropy changes and concurrence entanglement is discussed. Our results show that the behavior of the entropy change in agreement with the behavior of the concurrence to measure the entanglement between two subsystem structures. 相似文献
107.
Cun Zhu Rui Deng Jie Zeng Gamal E. Khalil Dana Dabiri Zhongze Gu Younan Xia 《Particle & Particle Systems Characterization》2013,30(6):542-548
A facile approach to the synthesis of pressure and temperature dual‐responsive polystyrene (PS) microbeads with controlled sizes via dispersion polymerization is described. Three different luminophors are selected and directly introduced into the reaction system and thus incorporated into the resultant PS microbeads during polymerization. By manipulating the reaction conditions, including concentrations of the initiator and monomer, polarity of the reaction medium, and injection rate for the monomer, uniform PS microbeads with sizes ranging from 1 to 5 μm are obtained. When a light source centered at 365 nm is used to excite all the luminophors in the PS beads, three distinct and resolvable emission peaks corresponding well with the luminophors are observed. By taking advantage of their sensitive responses to both pressure and temperature, the PS beads can be utilized for quantitative measurements of these two stimulations simultaneously. The PS beads loaded with multiple luminophors have the ability to serve as building blocks for the fabrication of novel sensing and imaging devices and therefore provide a promising strategy for the study of aerodynamics. 相似文献
108.
109.
Comparison of the lattice mode region of the low-temperature Raman spectrum of MCH and MCH-d14 under various cooling rates shows that there are two crystalline modifications. The molecular mode region frequencies however, remain invariant to cooling rate suggesting a single molecular conformation for both crystalline phases. 相似文献
110.
The resonant frequencies and mode shapes of contralateral femurs have been identified by experimental and analytical procedures. Also, the cross-sectional area, centroid, and principal moments of inertia were computed throughout the femur length for both compact and cancellous bone. The resonant frequencies of freely vibrating specimens were identified from transfer function measurements by using a Fourier analyzer. Twenty frequencies were noted in a frequency range of 20 Hz–8 kHz. A mathematical model of the femur consisting of 59 joined uniform segments, with each composed of compact and/or cancellous bone, was analyzed by using a transfer matrix technique. Results of the model enabled classification of the experimental resonances into deformations corresponding to flexure (about principal planes of inertia), torsion, and longitudinal extension with fundamental frequencies at 250, 308, 557, and 2138 Hz, respectively. Generalized non-dimensional resonant frequencies were computed based on femur geometry averaged over its length and compared with those predicted by simple beam models. This analysis provided further understanding of the vibrational behavior of the femur. 相似文献