全文获取类型
收费全文 | 611篇 |
免费 | 14篇 |
国内免费 | 3篇 |
专业分类
化学 | 368篇 |
晶体学 | 5篇 |
力学 | 37篇 |
数学 | 116篇 |
物理学 | 102篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 24篇 |
2018年 | 9篇 |
2017年 | 8篇 |
2016年 | 28篇 |
2015年 | 17篇 |
2014年 | 24篇 |
2013年 | 44篇 |
2012年 | 33篇 |
2011年 | 37篇 |
2010年 | 24篇 |
2009年 | 16篇 |
2008年 | 37篇 |
2007年 | 39篇 |
2006年 | 36篇 |
2005年 | 34篇 |
2004年 | 26篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1936年 | 2篇 |
1907年 | 1篇 |
1906年 | 2篇 |
1905年 | 1篇 |
1903年 | 1篇 |
1877年 | 1篇 |
1868年 | 1篇 |
排序方式: 共有628条查询结果,搜索用时 125 毫秒
611.
Marcelli T van Maarseveen JH Hiemstra H 《Angewandte Chemie (International ed. in English)》2006,45(45):7496-7504
In the steadily expanding field of organocatalysis, cinchona alkaloids play a prominent role. Until the late 1990s, bifunctional catalysts based on this scaffold relied exclusively on the C9-hydroxy group as the hydrogen-bond donor. Recently, new cinchona catalysts have been developed that feature a phenolic OH group in the C6' position-a structural feature that allows a diverse set of reactions to be catalyzed in a highly stereoselective fashion. This Minireview describes the scope and modes of action of this new class of asymmetric bifunctional organocatalysts. 相似文献
612.
Stener M Di Tommaso D Fronzoni G Decleva P Powis I 《The Journal of chemical physics》2006,124(2):024326
In the present work the photoelectron circular dichroism of camphor has been theoretically studied using B-spline and continuum multiple scattering-Xalpha methods, and comparisons are made with available experimental data. In general, rather large dichroism effects have been found for both valence and core (O 1s, C 1s) photoionizations. The agreement between the two calculations reported here and previous experimental measurements for core C 1s data is essentially quantitative. For valence ionization satisfactory agreement between theory and experiment has been obtained and the discrepancies have been attributed to both exchange-correlation potential limitations and the absence of response effects in the adopted formalism. The calculations predict, moreover, important features in the cross-section profiles, which have been discussed in terms of dipole-prepared continuum orbitals. 相似文献
613.
This contribution reports the results obtained in the definition of a catalytic method for the nucleophilic ring opening of epoxides by activated methylenes promoted by a polymer-supported base. The attention has been focused on the use of polymer supported bases and the best results have been obtained by using 4-(dimethylamino)pyridine (PS-DMAP) and 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine both on polystyrene (PS-BEMP). Solvent-free conditions has been essential for reaching a sufficient reactivity to realize this process, in fact when a reaction medium is used, the processes are almost unfeasible. 相似文献
614.
N-acyl-homoserine-lactones (AHSLs) are widely conserved signal molecules present in quorum sensing systems of Gram-negative bacteria such as Pseudomonas aeruginosa. We present here the results obtained with a hybrid linear trap/Fourier transform ion cyclotron resonance (LTQ-FTICR) mass spectrometer used to investigate the occurrence of AHSLs and cognate N-acyl-homoserines (AHSs) in bacterial isolates of P. aeruginosa (strain PAO1). Two hydrolysed AHSs were found in significant amounts, most likely formed through the lactone opening of N-3-oxo-decanoyl-L-homoserine-lactone (3OC10-HSL) and N-3-oxo-dodecanoyl-L-homoserine-lactone (3OC12-HSL). Structure elucidation of these ring-opened molecules, i.e. N-3-oxo-decanoyl-L-homoserine (3OC10-HS), and N-3-oxo-dodecanoyl-L-homoserine (3OC12-HS), which are not detected by bacterial biosensors, was performed by high-resolution and accurate mass measurements upon liquid chromatography (LC) and confirmed by tandem MS in the LTQ analyser. Assignment of chemical formula, with mass spectra in the form of [M+H]+, was significantly expedited by extracted ion chromatograms (XICs) because the number of potentially plausible formulae for each protonated signalling molecule was considerably reduced a priori by the LC behaviour, the high mass measurement accuracy available in FTICR mass spectra and the isotopic patterns. At least two concentration levels were observed in spent culture supernatants of P. aeruginosa: compounds at a relatively high content (5-15 microM) that is C4-HSL, 3OC10-HS, and 3OC12-HS and those occurring at a lower content (<0.2 microM) that is C6-HSL and C8-HSL. The implications of this work extend to a great variety of Gram-negative bacteria. 相似文献
615.
616.
Every 1‐rotational solution of a classic or twofold Oberwolfach problem (OP) of order n is generated by a suitable 2‐factor (starter) of or , respectively. It is shown that any starter of a twofold OP of order n gives rise to a starter of a classic OP of order (doubling construction). It is also shown that by suitably modifying the starter of a classic OP, one may obtain starters of some other OPs of the same order but having different parameters. The combination of these two constructions leads to lots of new infinite classes of solvable OPs. Still more classes can be obtained with the help of a third construction making use of the possible gracefulness of a graph whose connected components are cycles and at most one path. As one of the many applications, Hilton and Johnson's [J London Math Soc, 64 (2001) 513–522] bound about the solvability of OP is improved to in the case of r even. © 2012 Wiley Periodicals, Inc. J. Combin. Designs 20: 483‐503, 2012 相似文献
617.
Di Tommaso A. Neubauer U. Pantuso A. Rostasy F. S. 《Mechanics of Composite Materials》2001,37(4):327-338
This paper presents an evaluation of the results obtained from an initial study carried out at the IBMB, Technical University of Braunschweig, on the influence of temperature on adhesively bonded plate-concrete joint systems. The results of a theoretical model are also presented. The type of specimen used in this study is a three-point bending beam. The concrete specimens were prismatic in form, 100 × 100 × 700 mm without an internal steel reinforcement, strengthened at the intradoss with two types of UD CFRP lamina 20 mm wide and 590 mm long of thickness 1.4 mm for the E = 300 GPa type and 1.24 mm for the E = 175 GPa type. The plate-bonded specimens were designed to produce bending failure under a load, by not bonding the lamina and the concrete around the midspan of the specimens. The specimens were tested to failure at –100°, –30°, and +40°C after an approximately homogeneous temperature distribution within the concrete specimen has been reached. For comparison only, specimens of the same type were tested to failure at room temperature. The results obtained showed varying behavior of the bonded plate-concrete joint depending on variations in temperature. Furthermore, they showed different failure mechanisms. Greater reductions in the ultimate bond force were recorded for the test specimens strengthened with lamina having a high elastic modulus. A reasonable correlation was found between the experimental and theoretical results. 相似文献
618.
An in situ attenuated total reflection study of the chiral solid-liquid interface created by cinchonidine adsorption on a Pt/Al(2)O(3) model catalyst is presented. Experiments were performed in the presence of dissolved hydrogen, that is under conditions used for the heterogeneous enantioselective hydrogenation of alpha-functionalized ketones. Cinchonidine adsorbs via the quinoline moiety. The adsorption mode is coverage dependent and several species coexist on the surface. At low concentration (10(-6)M) a predominantly flat adsorption mode prevails. At increasing coverage two different tilted species, alpha-H abstracted and N lone pair bonded cinchonidine, are observed. The latter is only weakly bound and in a fast dynamic equilibrium with dissolved cinchonidine. At high concentration (10(-4)-10(-3) M) all three species coexist on the Pt surface. A slow transition from an adsorbate layer with a high fraction of alpha-H abstracted cinchonidine to one with a high fraction of N lone pair bonded cinchonidine is observed with the cinchonidine concentration being the driving force for the process. The reverse transition in the absence of dissolved cinchonidine is fast. Cinchonidine competes with solvent decomposition products for adsorption sites on the Pt, which may contribute to the observed solvent dependence of the heterogeneous enantioselective hydrogenation of ketones by cinchonidine-modified Pt. 相似文献
619.
Sara Gmez Natalia Rojas-Valencia Tommaso Giovannini Albeiro Restrepo Chiara Cappelli 《Molecules (Basel, Switzerland)》2022,27(2)
We unravel the potentialities of resonance Raman spectroscopy to detect ibuprofen in diluted aqueous solutions. In particular, we exploit a fully polarizable quantum mechanics/molecular mechanics (QM/MM) methodology based on fluctuating charges coupled to molecular dynamics (MD) in order to take into account the dynamical aspects of the solvation phenomenon. Our findings, which are discussed in light of a natural bond orbital (NBO) analysis, reveal that a selective enhancement of the Raman signal due to the normal mode associated with the C–C stretching in the ring, , can be achieved by properly tuning the incident wavelength, thus facilitating the recognition of ibuprofen in water samples. 相似文献
620.
Takashi Arima Maria Cristina Carrisi Sebastiano Pennisi Tommaso Ruggeri 《Entropy (Basel, Switzerland)》2022,24(1)
A relativistic version of the rational extended thermodynamics of polyatomic gases based on a new hierarchy of moments that takes into account the total energy composed by the rest energy and the energy of the molecular internal mode is proposed. The moment equations associated with the Boltzmann–Chernikov equation are derived, and the system for the first 15 equations is closed by the procedure of the maximum entropy principle and by using an appropriate BGK model for the collisional term. The entropy principle with a convex entropy density is proved in a neighborhood of equilibrium state, and, as a consequence, the system is symmetric hyperbolic and the Cauchy problem is well-posed. The ultra-relativistic and classical limits are also studied. The theories with 14 and 6 moments are deduced as principal subsystems. Particularly interesting is the subsystem with 6 fields in which the dissipation is only due to the dynamical pressure. This simplified model can be very useful when bulk viscosity is dominant and might be important in cosmological problems. Using the Maxwellian iteration, we obtain the parabolic limit, and the heat conductivity, shear viscosity, and bulk viscosity are deduced and plotted. 相似文献