全文获取类型
收费全文 | 1770篇 |
免费 | 262篇 |
国内免费 | 282篇 |
专业分类
化学 | 994篇 |
晶体学 | 22篇 |
力学 | 314篇 |
综合类 | 20篇 |
数学 | 196篇 |
物理学 | 768篇 |
出版年
2024年 | 3篇 |
2023年 | 17篇 |
2022年 | 46篇 |
2021年 | 47篇 |
2020年 | 76篇 |
2019年 | 57篇 |
2018年 | 57篇 |
2017年 | 58篇 |
2016年 | 78篇 |
2015年 | 74篇 |
2014年 | 107篇 |
2013年 | 147篇 |
2012年 | 103篇 |
2011年 | 106篇 |
2010年 | 89篇 |
2009年 | 116篇 |
2008年 | 108篇 |
2007年 | 115篇 |
2006年 | 114篇 |
2005年 | 78篇 |
2004年 | 88篇 |
2003年 | 74篇 |
2002年 | 71篇 |
2001年 | 57篇 |
2000年 | 62篇 |
1999年 | 45篇 |
1998年 | 46篇 |
1997年 | 37篇 |
1996年 | 47篇 |
1995年 | 30篇 |
1994年 | 20篇 |
1993年 | 20篇 |
1992年 | 23篇 |
1991年 | 19篇 |
1990年 | 5篇 |
1989年 | 14篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 4篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1982年 | 2篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有2314条查询结果,搜索用时 15 毫秒
41.
42.
It is shown that for , there exists an optimal packing with triples on points that contains no Pasch configurations. Furthermore, for all (mod 6), there exists a pairwise balanced design of order , whose blocks are all triples apart from a single quintuple, and that has no Pasch configurations amongst its triples. 相似文献
43.
For the first time, high-level structural and rovibrational data are provided for the hyroxyethynyl anion, CCOH?. CCOH? is a promising molecule for interstellar detection even though no new anions have been observed in the interstellar medium for the past half-decade. The large dipole moment of the corresponding neutral radical may be key for its creation as has been hypothesised and supported for other anions known to exist in various astronomical environments. Highly accurate quartic force fields are employed where previous benchmarks have produced spectroscopic constants and anharmonic vibrational frequencies within 20 MHz and 1 cm?1, respectively, of experiment. This same approach is applied here for CCOH? and its deuterated isotopologue with the goal of assisting laboratory experiments and/or astronomical observers in the potential detection of this anion. 相似文献
44.
Nobumasa Kamigata 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):667-678
Abstract The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied. 相似文献
45.
Türsen Demir Frederick J. Raveney Robert A. Shaw 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):155-163
Abstract The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl]aniline with phosphorus oxychloride, thiophosphoryl chloride, and their derivatives yield 1,3,2-benzodiazaphosphorine 2-oxides and 2-sulphides. Their 1H NMR and infrared spectra are discussed. Related 1,3,2-benzodiazophosphorine and 1,3,2-dibenzodiazaphosphocine 2-oxides and 2-sulphides are compared. 相似文献
46.
A facile and efficient synthetic method of esters from their corresponding carboxylic acids and amino acids is described. The esterification reaction of carboxylic acids and amino acids could be greatly accelerated under microwave irradiation because the reactions described in this article took place in only 5 min with almost quantitative yields, and distinct acidity of catalytic acids was well tolerated. Unlike the racemation problem in microwave-assisted N-acylation reactions, the esters of chiral amino acids could be achieved with retention of configuration under this condition. 相似文献
47.
Depending on their relative orientation, coupled oscillating carbonyl groups provide a VCD spectrum with a characteristic CO bond stretching region showing a strong bisignate VCD feature, which can be readily predicted adopting long available semiempirical methods. The extended coupled oscillator (ECO) formalism has been used to assign the absolute configuration of a recently synthesized chiral 3-substituted isoindolinone. The prediction of (S) configuration for the (−) enantiomer has been confirmed by quantum mechanical calculations. 相似文献
48.
Yu‐Sheng Su Dr. Yongzhu Fu Dr. Bingkun Guo Dr. Sheng Dai Prof. Arumugam Manthiram 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8621-8626
The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S8?Li2S4), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li2S2 and Li2S (Li2S4?Li2S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications. 相似文献
49.
Dong-Bao Hu Wen-Xin Li Zhen-Zhu Zhao Tao Feng Rong-Hua Yin Zheng-Hui Li Ji-Kai Liu Hua-Jie Zhu 《Tetrahedron letters》2014
Four new highly unsaturated pyranone derivatives A–D (1–4), together with one known compound 5 (−)-nitidon were isolated from cultures of the fungus Junghuhnianitida. Planar structures of the new compounds were elucidated on the basis of extensive NMR spectroscopic and mass spectrometric analyses. Absolute configurations of the new compounds were determined on the basis of biosynthetic considerations and quantum chemistry theory. Compound 1 exhibited almost the same cytotoxic activities as cis-platin. 相似文献
50.
Neomacrophorins I (1), II (2), and III (3) were isolated from the culture broth of Trichoderma sp. 1212-03, which was collected at Shirakami Mountainous area in Japan. Structural analyses disclosed that these resemble known macrophorins but possess axial-hydroxy group at C3 as well as different side chains at C7′. These are diastereomeric forms of macrophorins for 5′,6′-epoxide functionality. The NMR analyses suggested their relative configurational relationship between the C1–C15 drimene and C1′–C7′ epoxyquinone moieties. ECD spectral discussions verified them particularly for C5′,C6′-epoxyquinone (1), C5′,C6′-epoxysemiquinone (2 and 3), and 2″,3″-dihydroxybutanoate moiety in 1 and 2. The configuration of C3″-stereocenter of 3 was determined by chiral GC–MS after converting into methyl (S)-3″-hydroxybutanoate by basic of 3 methanolysis. Biological assays disclosed that 1 induces hyphal branching of Cochliobolus miyabeanus as well as cytotoxicity against human colorectal cancer COLO 201. 相似文献