全文获取类型
收费全文 | 2154篇 |
免费 | 89篇 |
国内免费 | 10篇 |
专业分类
化学 | 1336篇 |
晶体学 | 13篇 |
力学 | 98篇 |
数学 | 286篇 |
物理学 | 520篇 |
出版年
2023年 | 25篇 |
2022年 | 59篇 |
2021年 | 74篇 |
2020年 | 52篇 |
2019年 | 64篇 |
2018年 | 56篇 |
2017年 | 45篇 |
2016年 | 103篇 |
2015年 | 61篇 |
2014年 | 100篇 |
2013年 | 135篇 |
2012年 | 165篇 |
2011年 | 153篇 |
2010年 | 99篇 |
2009年 | 79篇 |
2008年 | 124篇 |
2007年 | 125篇 |
2006年 | 106篇 |
2005年 | 95篇 |
2004年 | 80篇 |
2003年 | 44篇 |
2002年 | 42篇 |
2001年 | 33篇 |
2000年 | 34篇 |
1999年 | 17篇 |
1998年 | 15篇 |
1997年 | 15篇 |
1996年 | 21篇 |
1995年 | 14篇 |
1994年 | 24篇 |
1993年 | 24篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 11篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1982年 | 9篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1974年 | 7篇 |
1973年 | 7篇 |
1972年 | 4篇 |
排序方式: 共有2253条查询结果,搜索用时 15 毫秒
1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
3.
B. Savo P. Romano A. Nigro R. Di Leo 《Physica C: Superconductivity and its Applications》2002,370(4):275-280
The flat voltage noise component of current biased, high-transparency Nb/AlOx/Nb superconducting tunnel junctions has been investigated at frequencies up to 70 kHz. Several aspects of the analyzed phenomena suggest the presence of current noise effects induced by the discreteness of the charge carriers. At subgap voltages, where excess currents occur, a behavior coherent with a multiple Andreev reflection-assisted transport through the tunnel barrier has been found. However, the measured charge values exceed any theoretical prediction. 相似文献
4.
René Meziat Diego Patiño Pablo Pedregal 《Computational Optimization and Applications》2007,38(1):147-171
We propose an alternative method for computing effectively the solution of non-linear, fixed-terminal-time, optimal control
problems when they are given in Lagrange, Bolza or Mayer forms. This method works well when the nonlinearities in the control
variable can be expressed as polynomials. The essential of this proposal is the transformation of a non-linear, non-convex
optimal control problem into an equivalent optimal control problem with linear and convex structure. The method is based on
global optimization of polynomials by the method of moments. With this method we can determine either the existence or lacking
of minimizers. In addition, we can calculate generalized solutions when the original problem lacks of minimizers. We also
present the numerical schemes to solve several examples arising in science and technology. 相似文献
5.
A model for the interaction of near-infrared laser pulses with metal powders in selective laser sintering 总被引:4,自引:0,他引:4
P. Fischer N. Karapatis V. Romano R. Glardon H.P. Weber 《Applied Physics A: Materials Science & Processing》2002,74(4):467-474
A thermal model of the interaction of pulsed near-infrared laser radiation from a Nd:YAG laser was made, taking the measured
powder properties such as reflectance, optical penetration depth and thermal conductivity into account. It allows an estimation
of the evolution of two different temperatures: the average temperature of the powder (taken over the grains in a volume given
by the laser beam diameter and the optical penetration depth) and the temperature distinction within a single grain. It showed
that in pulsed mode consolidation can be achieved at much lower average power as the surface of the powder particles are molten
but their cores remain at nearly room temperature. This leads to a much lower average temperature and therefore a dramatic
decrease in residual thermal stresses in the finished piece. The results of the model were experimentally tested and confirmed.
Received: 26 July 2001 / Accepted: 23 November 2001 / Published online: 23 January 2002 相似文献
6.
Jürgen Kurths M. Carmen Romano Marco Thiel Grigory V. Osipov Mikhail V. Ivanchenko István Z. Kiss John L. Hudson 《Nonlinear dynamics》2006,44(1-4):135-149
We present two different approaches to detect and quantify phase synchronization in the case of coupled non-phase coherent
oscillators. The first one is based on the general idea of curvature of an arbitrary curve. The second one is based on recurrences
of the trajectory in phase space. We illustrate both methods in the paradigmatic example of the R?ssler system in the funnel
regime. We show that the second method is applicable even in the case of noisy data. Furthermore, we extend the second approach
to the application of chains of coupled systems, which allows us to detect easily clusters of synchronized oscillators. In
order to illustrate the applicability of this approach, we show the results of the algorithm applied to experimental data
from a population of 64 electrochemical oscillators. 相似文献
7.
This Letter considers the generalized second law of gravitational thermodynamics in two scenarios featuring a phantom dominated expansion plus a black hole. The law is violated in both scenarios. 相似文献
8.
The electrophilic α-alkylation of ketones with alcohols was accomplished by a [Ru(DMSO)4]Cl2 catalyzed process, water being the only wasted material. The reaction can be successfully governed to produce either the expected ketones or their related alcohols only by changing the reaction conditions. When 2-aminobenzyl alcohol was used, a cyclization process took place to yield 2,3-disubstituted quinolines. 相似文献
9.
Visintin RF Lapasin R Vignati E D'Antona P Lockhart TP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6240-6249
A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported. 相似文献
10.
Fluorescent behavior of B-phycoerythrin in microemulsions of aerosol OT/water/isooctane 总被引:3,自引:0,他引:3
Bermejo R Tobaruela DJ Talavera EM Orte A Alvarez-Pez JM 《Journal of colloid and interface science》2003,263(2):616-624
Taking advantage of its unusual fluorescent properties, the incorporation of B-phycoerythrin (B-PE) in aerosol OT (AOT, sodium bis-(2-ethylhexyl) sulphosuccinate)/water/isooctane microemulsions was investigated by following their steady-state and time-resolved fluorescence as a function of the water-to-surfactant molar ratio, w(0). The fluorescent intensity at 575 nm increased continuously with increasing water content, saturating at a w(0) around 35 and staying practically constant at w(0)> or =40. The steady-state anisotropy showed an initial increase with increasing water content until w(0)=23 and then decreased strongly, staying practically constant when w(0)> or =40. The values of the fluorescent parameters, anisotropy and fluorescent intensity, were unchanged when the water content of the system increased in the range between w(0)=40 to 50. This implies the effective incorporation of B-PE in the microemulsion droplets with w(0)> or =40, as well as the equilibrium of the dispersion at these water/surfactant ratios, since higher water content does not affect the main surrounding microenvironment of the protein. The overall incorporation in the microemulsion droplets caused minor spectroscopic changes with respect to biliprotein in aqueous solution of 20 mM sodium phosphate buffer, pH 7.0, such as a blue absorption shift of 3 nm and an emission shift of 1.5 nm, as well as a slight increase in excitation anisotropy spectrum mainly caused by a decrease in protein mobility. Therefore, there are no important interactions between the chromophores and the AOT sulfonate head groups. Emission intensity decays followed complex kinetics in both aqueous and dispersion media. The stability with time and temperature of the biliprotein in the microemulsion was higher than in the aqueous solution. All the results can be explained in terms of B-PE inclusion in the water droplets of AOT microemulsions where the protein has similar configuration and conformation to that in aqueous solution but with the chromophores more protected. 相似文献