全文获取类型
收费全文 | 8635篇 |
免费 | 429篇 |
国内免费 | 5篇 |
专业分类
化学 | 6637篇 |
晶体学 | 48篇 |
力学 | 167篇 |
数学 | 1228篇 |
物理学 | 989篇 |
出版年
2023年 | 76篇 |
2022年 | 52篇 |
2021年 | 76篇 |
2020年 | 136篇 |
2019年 | 159篇 |
2018年 | 157篇 |
2017年 | 171篇 |
2016年 | 342篇 |
2015年 | 307篇 |
2014年 | 338篇 |
2013年 | 609篇 |
2012年 | 715篇 |
2011年 | 780篇 |
2010年 | 433篇 |
2009年 | 319篇 |
2008年 | 678篇 |
2007年 | 644篇 |
2006年 | 533篇 |
2005年 | 530篇 |
2004年 | 430篇 |
2003年 | 335篇 |
2002年 | 290篇 |
2001年 | 67篇 |
2000年 | 62篇 |
1999年 | 66篇 |
1998年 | 43篇 |
1997年 | 53篇 |
1996年 | 70篇 |
1995年 | 41篇 |
1994年 | 29篇 |
1993年 | 35篇 |
1992年 | 28篇 |
1991年 | 29篇 |
1990年 | 27篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 23篇 |
1986年 | 34篇 |
1985年 | 40篇 |
1984年 | 40篇 |
1983年 | 25篇 |
1982年 | 30篇 |
1981年 | 34篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 8篇 |
1977年 | 11篇 |
1976年 | 9篇 |
1975年 | 11篇 |
1974年 | 9篇 |
排序方式: 共有9069条查询结果,搜索用时 62 毫秒
11.
12.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
13.
14.
15.
Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties 下载免费PDF全文
Ismael Gracia Beatriz Feringán Prof. José Luis Serrano Dr. Roberto Termine Dr. Attilio Golemme Dr. Ana Omenat Prof. Joaquín Barberá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):1359-1369
The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role. 相似文献
16.
Partial Oxidation as a Rational Approach to Kinetic Control in Bioinspired Magnetite Synthesis 下载免费PDF全文
Dr. Cem L. Altan Jos J. M. Lenders Paul H. H. Bomans Prof. Gijsbertus de With Dr. Heiner Friedrich Dr. Seyda Bucak Prof. Nico A. J. M. Sommerdijk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6150-6156
Biological systems show impressive control over the shape, size and organization of mineral structures, which often leads to advanced physical properties that are tuned to the function of these materials. Such control is also found in magnetotactic bacteria, which produce—in aqueous medium and at room temperature—magnetite nanoparticles with precisely controlled morphologies and sizes that are generally only accessible in synthetic systems with the use of organic solvents and/or the use of high‐temperature methods. The synthesis of magnetite under biomimetic conditions, that is, in water and at room temperature and using polymeric additives as control agents, is of interest as a green production method for magnetic nanoparticles. Inspired by the process of magnetite biomineralization, a rational approach is taken by the use of a solid precursor for the synthesis of magnetite nanoparticles. The conversion of a ferrous hydroxide precursor, which we demonstrate with cryo‐TEM and low‐dose electron diffraction, is used to achieve control over the solution supersaturation such that crystal growth can be regulated through the interaction with poly‐(α,β)‐dl ‐aspartic acid, a soluble, negatively charged polymer. In this way, stable suspensions of nanocrystals are achieved that show remanence and coercivity at the size limit of superparamagnetism, and which are able to align their magnetic moments forming strings in solution as is demonstrated by cryo‐electron tomography. 相似文献
17.
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
18.
19.
Sara Trujillo Estela Pérez‐Román Apostolos Kyritsis José Luis Gómez Ribelles Christos Pandis 《Journal of Polymer Science.Polymer Physics》2015,53(19):1391-1400
Novel biomaterials are needed for bone tissue repair with improved mechanical performance compared to classical bioceramics. The objective of this work was to characterize a hybrid filler material, which is capable to coat as a thin film porous scaffolds improving their mechanical properties for bone tissue engineering. The hybrid filler material is a blend of chitosan and silica network formed through in situ sol–gel using tetraethylortosilicate and 3‐glycidoxypropyltrimethoxysilane (GPTMS) as silica precursors. The hypothesis was that the epoxy ring of GPTMS could react with the amino groups of chitosan in acidic media while it is also reacting the siloxane groups of hydrolyzed silica precursors. The formation of the hybrid organic–inorganic network was assessed by different physical techniques revealing changes in molecular mobility and hydrophilicity upon chemical reaction. Finally, the cytotoxicity of the samples was also evaluated by MTT assay. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1391–1400 相似文献