全文获取类型
收费全文 | 2356篇 |
免费 | 64篇 |
国内免费 | 20篇 |
专业分类
化学 | 1432篇 |
晶体学 | 11篇 |
力学 | 37篇 |
数学 | 425篇 |
物理学 | 535篇 |
出版年
2023年 | 17篇 |
2022年 | 48篇 |
2021年 | 64篇 |
2020年 | 49篇 |
2019年 | 66篇 |
2018年 | 62篇 |
2017年 | 54篇 |
2016年 | 79篇 |
2015年 | 90篇 |
2014年 | 76篇 |
2013年 | 160篇 |
2012年 | 136篇 |
2011年 | 162篇 |
2010年 | 112篇 |
2009年 | 114篇 |
2008年 | 164篇 |
2007年 | 141篇 |
2006年 | 171篇 |
2005年 | 137篇 |
2004年 | 92篇 |
2003年 | 82篇 |
2002年 | 90篇 |
2001年 | 36篇 |
2000年 | 28篇 |
1999年 | 28篇 |
1998年 | 22篇 |
1997年 | 24篇 |
1996年 | 32篇 |
1995年 | 15篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1969年 | 3篇 |
排序方式: 共有2440条查询结果,搜索用时 0 毫秒
171.
Hybrid density functional theory has been applied for investigations of the electronic and atomic structure of bulk phases, nanolayers, and nanotubes based on titanium and zirconium disulfides. Calculations have been performed on the basis of the localized atomic functions by means of the CRYSTAL‐2009 computer code. The full optimization of all atomic positions in the regarded systems has been made to study the atomic relaxation and to determine the most favorable structures. The different layered and isotropic bulk phases have been considered as the possible precursors of the nanotubes. Calculations on single‐walled TiS2 and ZrS2 nanotubes confirmed that the nanotubes obtained by rolling up the hexagonal crystalline layers with octahedral 1T morphology are the most stable. The strain energy of TiS2 and ZrS2 nanotubes is small, does not depend on the tube chirality, and approximately obeys to D–2 law (D is nanotube diameter) of the classical elasticity theory. It is greater than the strain energy of the similar TiO2 and ZrO2 nanotubes; however, the formation energy of the disulfide nanotubes is considerably less than the formation energy of the dioxide nanotubes. The distance and interaction energy between the single‐wall components of the double‐wall nanotubes is proved to be close to the distance and interaction energy between layers in the layered crystals. Analysis of the relaxed nanotube shape using radial coordinate of the metal atoms demonstrates a small but noticeable deviation from completely cylindrical cross‐section of the external walls in the armchair‐like double‐wall nanotubes. © 2013 Wiley Periodicals, Inc. 相似文献
172.
Unprecedented 1,14‐seco‐Crotofolanes from Croton insularis: Oxidative Cleavage of Crotofolin C by a Putative Homo‐Baeyer–Villiger Rearrangement 下载免费PDF全文
Dr. Lidiya A. Maslovskaya Dr. Andrei I. Savchenko Carly J. Pierce Dr. Victoria A. Gordon Dr. Paul W. Reddell Prof. Peter G. Parsons Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14226-14230
EBC‐162 isolated from Croton insularis, obtained from the northern rainforest of Australia, was structurally affirmed as crotofolin C ( 4 ). Novel oxidative degradation products, EBC‐233 and EBC‐300, which are the first crotofolane endoperoxides, were also isolated. Both endoperoxides were found to be stable intermediates, which are proposed to undergo an unprecedented homo‐Baeyer–Villiger biosynthetic rearrangement to give a new class of 1,14‐seco‐crotofolane diterpenes. Prolonged storage of all isolates assisted in authenticating their natural product status. Anticancer activities of reported compounds are presented. 相似文献
173.
Kirill V. Zaitsev Yulia A. Piskun Yuri F. Oprunenko Sergey S. Karlov Galina S. Zaitseva Irina V. Vasilenko Andrei V. Churakov Sergei V. Kostjuk 《Journal of polymer science. Part A, Polymer chemistry》2014,52(9):1237-1250
The aluminum complexes containing two iminophenolate ligands of the type (p‐XC6H4NCHC6H4O‐o)2AlR' (R′=Me ( 3, 4 ) or R′=O(CH2)4OCH=CH2 ( 5, 6 ), X=H ( 3, 5 ), F( 4, 6 )) were synthesized and characterized by 1H, 13C NMR spectroscopy, and X‐ray crystallography. The reaction of AlMe3 with two equivalents of substituted iminophenols gave five‐coordinated {ONR}2AlMe ( 3, 4 ) complexes. Subsequent reaction of these methyl complexes with unsaturated alcohol, HO(CH2)4OCH=CH2, resulted in target compounds 5 and 6 in a good yield. It was shown that the complexes ( 3 ‐ 6 ) are monomeric in solution (NMR) and in solid state (X‐ray analysis). The catalytic activity of the complexes 5 and 6 towards ring‐opening polymerization (ROP) of ?‐caprolactone and d,l ‐lactide was assessed. Complex 5 showed higher activity as compared with 6 , while both of these catalysts induced controlled homo‐ and copolymerization to afford the macromonomers with high content of vinyl ether end groups (Fn > 80%) in a broad range of molecular weights (Mn = 4000–30,000 g mol?1) with relatively narrow MWD (Mw/Mn = 1.1–1.5). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1237–1250 相似文献
174.
Eva Vergucht Björn De Samber Andrei Izmer Bart Vekemans Karen Appel Sergei Tolmachev Laszlo Vincze Frank Vanhaecke 《Analytical and bioanalytical chemistry》2015,407(6):1559-1566
This study aims at evaluating the capabilities of synchrotron radiation micro X-ray fluorescence spectrometry (SR micro-XRF) for qualitative and semi-quantitative elemental mapping of the distribution of actinides in human tissues originating from individuals with documented occupational exposure. The investigated lymph node tissues were provided by the United States Transuranium and Uranium Registries (USTUR) and were analyzed following appropriate sample pre-treatment. Semi-quantitative results were obtained via calibration by external standards and demonstrated that the uranium concentration level in the detected actinide hot spots reaches more than 100 μg/g. For the plutonium hot spots, concentration levels up to 31 μg/g were found. As illustrated by this case study on these unique samples, SR micro-XRF has a high potential for this type of elemental bio-imaging owing to its high sensitivity, high spatial resolution, and non-destructive character.
?
相似文献
175.
Andrei K. Yudin 《Chemical science》2015,6(1):30-49
A noticeable increase in molecular complexity of drug targets has created an unmet need in the therapeutic agents that are larger than traditional small molecules. Macrocycles, which are cyclic compounds comprising 12 atoms or more, are now recognized as molecules that “are up to the task” to interrogate extended protein interfaces. However, because macrocycles (particularly the ones based on peptides) are equipped with large polar surface areas, achieving cellular permeability and bioavailability is anything but straightforward. While one might consider this to be the Achilles'' heel of this class of compounds, the synthetic community continues to develop creative approaches toward the synthesis of macrocycles and their site-selective modification. This perspective provides an overview of both mechanistic and structural issues that bear on macrocycles as a unique class of molecules. The reader is offered a historical foray into some of the classic studies that have resulted in the current renaissance of macrocycles. In addition, an attempt is made to overview the more recent developments that give hope that macrocycles might indeed turn into a useful therapeutic modality. 相似文献
176.
177.
Mihaela Pascu Daniela-Elena Pascu Gina Alina Trăistaru Aurelia Cristina Nechifor Andrei A. Bunaciu Hassan Y. Aboul-Enein 《Journal of the Iranian Chemical Society》2014,11(2):315-321
The present study investigates the antioxidant activities of some Romanian plants, using different spectrophotometric methods (FRAP I, FRAP II, and CUPRAC). The plants investigated are hawthorn (Crataegus oxyacantha), bilberry (Vaccinium myrtillus L.), rosehip (Rosa canina), and chokeberries (Aronia melanocarpa). Hawthorn is used to treat a wide variety of inflammatory conditions, but the primary use is generally restricted for treating hypertension, ischemic heart disease, congestive heart failure, and arrhythmia. Investigations have proved the safe and reliable use of plant and plant extracts for treatment of cardiovascular disorders. 相似文献
178.
179.
Prof. Dr. Konstantin V. Kudryavtsev Chia‐Chun Yu Polina M. Ivantcova Prof. Dr. Vladimir I. Polshakov Dr. Andrei V. Churakov Prof. Dr. Stefan Bräse Prof. Dr. Nikolay S. Zefirov Prof. Dr. Jih‐Hwa Guh 《化学:亚洲杂志》2015,10(2):383-389
Functionalized oligomeric organic compounds with well‐defined β‐proline scaffold have been synthesized by a cycloadditive oligomerization approach in racemic and enantiopure forms. The structure of the novel β‐peptides was investigated by NMR spectroscopic and X‐ray methods determining the conformational shapes of the β‐proline oligomers in solution and solid states. The main structural elements subject to conformational switches are β‐peptide bonds between 5‐arylpyrrolidine‐2‐carboxylic acid units existing in Z/E configurations. The whole library of short β‐peptides and intermediate acrylamides has been tested on antiproliferative activity towards the hormone‐refractory prostate cancer cell line PC‐3 revealing several oligomeric compounds with low micromolar and submicromolar activities. Bromine‐substituted dimeric and trimeric acrylamides induced caspase‐dependent apoptosis of PC‐3 cells through cell‐cycle arrest and mitochondrial damage. 相似文献
180.