全文获取类型
收费全文 | 3336篇 |
免费 | 159篇 |
国内免费 | 31篇 |
专业分类
化学 | 2379篇 |
晶体学 | 23篇 |
力学 | 46篇 |
数学 | 443篇 |
物理学 | 635篇 |
出版年
2023年 | 18篇 |
2022年 | 53篇 |
2021年 | 84篇 |
2020年 | 66篇 |
2019年 | 50篇 |
2018年 | 50篇 |
2017年 | 48篇 |
2016年 | 109篇 |
2015年 | 121篇 |
2014年 | 116篇 |
2013年 | 223篇 |
2012年 | 215篇 |
2011年 | 240篇 |
2010年 | 156篇 |
2009年 | 154篇 |
2008年 | 212篇 |
2007年 | 199篇 |
2006年 | 185篇 |
2005年 | 158篇 |
2004年 | 117篇 |
2003年 | 116篇 |
2002年 | 108篇 |
2001年 | 77篇 |
2000年 | 103篇 |
1999年 | 63篇 |
1998年 | 28篇 |
1997年 | 41篇 |
1996年 | 66篇 |
1995年 | 34篇 |
1994年 | 26篇 |
1993年 | 26篇 |
1992年 | 24篇 |
1991年 | 26篇 |
1990年 | 16篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1987年 | 7篇 |
1986年 | 17篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 19篇 |
1981年 | 7篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1976年 | 11篇 |
1974年 | 7篇 |
1973年 | 7篇 |
排序方式: 共有3526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.
3.
Sergio Ayala‐Mar Javier Donoso‐Quezada Roberto C. Gallo‐Villanueva Victor H. Perez‐Gonzalez Jos Gonzlez‐Valdez 《Electrophoresis》2019,40(23-24):3036-3049
Exosomes are nanovesicles secreted by most cellular types that carry important biochemical compounds throughout the body with different purposes, playing a preponderant role in cellular communication. Because of their structure, physicochemical properties and stability, recent studies are focusing in their use as nanocarriers for different therapeutic compounds for the treatment of different diseases ranging from cancer to Parkinson's disease. However, current bioseparation protocols and methodologies are selected based on the final exosome application or intended use and present both advantages and disadvantages when compared among them. In this context, this review aims to present the most important technologies available for exosome isolation while discussing their advantages and disadvantages and the possibilities of being combined with other strategies. This is critical since the development of novel exosome‐based therapeutic strategies will be constrained to the effectiveness and yield of the selected downstream purification methodologies for which a thorough understanding of the available technological resources is needed. 相似文献
4.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
5.
6.
G. Montero L. Gonzlez E. Flrez M. D. García A. Surez 《Numerical Linear Algebra with Applications》2002,9(3):239-247
Parallel preconditioners are presented for the solution of general linear systems of equations. The computation of these preconditioners is achieved by orthogonal projections related to the Frobenius inner product. So, minM∈??∥AM?I∥ F and matrix M0∈?? corresponding to this minimum (?? being any vectorial subspace of ??n(?)) are explicitly computed using accumulative formulae in order to reduce computational cost when subspace ?? is extended to another one containing it. Every step, the computation is carried out taking advantage of the previous one, what considerably reduces the amount of work. These general results are illustrated with the subspace of matrices M such that AM is symmetric. The main application is developed for the subspace of matrices with a given sparsity pattern which may be constructed iteratively by augmenting the set of non‐zero entries in each column. Finally, the effectiveness of the sparse preconditioners is illustrated with some numerical experiments. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
7.
The interferometric intensity patterns from a 2D shearing interferometer are shown and discussed. The intensity patterns can be obtained in two different approaches incorporating differential and extended wavefront controlled displacements. The reliable directional sensitivity of this interferometer allows the optimization of the measurement parameters to estimate the wavefront of the intensity patterns by regularization techniques. 相似文献
8.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
9.
P. González D. Fernández J. Pou E. García J. Serra B. León M. Pérez-Amor T. Szörényi 《Applied Physics A: Materials Science & Processing》1993,57(2):181-185
A study of the gas-phase parameters involved in ArF laser induced chemical vapour deposition of silicon-oxide thin films is presented. A complete set of experiments has been performed showing the influence of the concentration of the precursor gases, N2O and SiH4, and their influence on total and partial pressures on film growth and properties. In this paper we demonstrate the ability of this LCVD method to deposit silicon oxide films of different compositions and densities by appropriate control of gas composition and total pressure. Moreover, a material specific calibration plot comprising data obtained using different preparation techniques is presented, allowing determination of the stoichiometry of SiO
x
films by using FTIR spectroscopy independently of the deposition method. For the range of processing conditions examined, the experimental results suggest that chemical processes governing deposition take place mainly in the gas phase. 相似文献
10.
A. Bonilla F. Pérez-González A. Stray R. Trujillo-González 《Journal d'Analyse Mathématique》1997,73(1):65-89
This paper is concerned with several approximation problems in the weighted Hardy spacesH
p(Ω) of analytic functions in the open unit disc D of the complex plane ℂ. We prove that ifX is a relatively closed subset of D, the class of uniform limits onX of functions inH
p(Ω) coincides, moduloH
p(Ω), with the space of uniformly continuous functions on a certain hull ofX which are holomorphic on its interior. We also solve the simultaneous approximation problems of describing Farrell and Mergelyan
sets forH
p(Ω), giving geometric characterizations for them. By replacing approximating polynomials by polynomial multipliers of outer
functions, our results lead to characterizations of the same sets with respect to cyclic vectors in the classical Hardy spacesH
p(D), 1 ⪯p < ∞.
Dedicated to Professor Nácere Hayek on the occasion of his 75th birthday. 相似文献