全文获取类型
收费全文 | 2750篇 |
免费 | 120篇 |
国内免费 | 22篇 |
专业分类
化学 | 2022篇 |
晶体学 | 35篇 |
力学 | 89篇 |
综合类 | 3篇 |
数学 | 185篇 |
物理学 | 558篇 |
出版年
2024年 | 17篇 |
2023年 | 36篇 |
2022年 | 115篇 |
2021年 | 151篇 |
2020年 | 73篇 |
2019年 | 101篇 |
2018年 | 82篇 |
2017年 | 74篇 |
2016年 | 143篇 |
2015年 | 98篇 |
2014年 | 115篇 |
2013年 | 196篇 |
2012年 | 216篇 |
2011年 | 220篇 |
2010年 | 119篇 |
2009年 | 107篇 |
2008年 | 126篇 |
2007年 | 117篇 |
2006年 | 117篇 |
2005年 | 114篇 |
2004年 | 81篇 |
2003年 | 74篇 |
2002年 | 49篇 |
2001年 | 23篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 14篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1981年 | 19篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1962年 | 3篇 |
排序方式: 共有2892条查询结果,搜索用时 187 毫秒
41.
Cao B Wakahara T Tsuchiya T Kondo M Maeda Y Aminur Rahman GM Akasaka T Kobayashi K Nagase S Yamamoto K 《Journal of the American Chemical Society》2004,126(30):9164-9165
A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5). 相似文献
42.
An easy, safe, and effective method for preparing (diacetoxyiodo)arenes from iodoarenes is presented. Addition of trifluoromethanesulfonic acid (triflic acid) as a promoter causes a drastic increase in the yield of (diacetoxyiodo)arenes in the reaction of iodoarenes with sodium perborate. The reaction of the iodoarenes with sodium perborate in acetic acid in the presence of triflic acid at 40-45 degrees C efficiently generates the corresponding (diacetoxyiodo)arenes in high yields within short time. 相似文献
43.
Yu-Ping Zhang Kwang-Pill Lee Hyun-Joo Noh Ali Md Showkat Seong-Ho Choi 《Microchemical Journal》2004,78(2):99-106
An appropriate optimization strategy should be used to find a desired resolution or selectivity with a minimum number of experiments in a limited time, which could assure the baseline separation of all target compounds. It was usually realized by means of a specialized computer program. In this paper, mapping optimization method and overlapping resolution mapping were compared for the optimization of a reversed-phase high-performance liquid chromatography (HPLC) isocratic separation of neutral compounds. The calculated resolutions and separation time of 7 to 10 experiments are fitted by different equations, which were used to build a contour plot with a minimum effective resolution and maximum retention time as a function of a mobile phase composition. The balance between resolution and analysis time could be easily realized by the overlapping of the final overlapping resolution mapping and analysis time mapping. The validity of the two methods was confirmed by some typical experiments. The models are simple, visual, and common without theoretical arithmetic. 相似文献
44.
Akhtaruzzaman M Kamata N Nishida J Ando S Tada H Tomura M Yamashita Y 《Chemical communications (Cambridge, England)》2005,(25):3183-3185
Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility. 相似文献
45.
Copper-catalyzed N-arylation of diazoles can be accomplished using air-stable CuI as a copper source and 1,10-phenanthroline in the presence of KF/Al2O3 as a base. This is a simple and efficient method for the coupling of aryl bromide with diazoles. Different functionalized aryl bromides were coupled with diazoles using this system. 相似文献
46.
An efficient route to various sugar lactones has been developed. Key to the overall transformation is the sequential osmium-catalyzed dihydroxylation of 2,4-dienoates. The simplest (one-step/racemic) example of this reaction occurs when the dihydroxylation is performed with aqueous NMO in MeOH. When the first dihydroxylation is performed using the AD-mix procedure, an enantioselective variant results. When a matched AD-mix procedure is used for the second dihydroxylation, an exceedingly diastereo- and enantioselective synthesis of galacto-1,4-lactone results. [Reaction: see text] 相似文献
47.
M. S. Rahman Khan 《Applied Physics A: Materials Science & Processing》1984,35(4):263-265
The resistivity of thin films (80–200 Å) of ErH2 increases sharply when heated for 2 h at 300 °C in vacuum in the presence of hydrogen gas at 10–2 Torr. This confirms that the films, originally metallic conductor, have become converted to semiconducting ErH3 which is in conformity with the structural studies. The negative values of TCR also indicate the semiconducting nature of the hydrogen treated films. Activation energies of the films have been evaluated. 相似文献
48.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
49.
Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide
A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10?6?1.0×10?4 M and 5.0×10?7 to 1.0×10?4 M, respectively. The detection limits were determined to be of 1.0×10?6 M and 9.0×10?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples. 相似文献
50.
Two-dimensional capillary electrophoresis was used for the separation of proteins and biogenic amines from the mouse AtT-20 cell line. The first-dimension capillary contained a TRIS–CHES–SDS–dextran buffer to perform capillary sieving electrophoresis, which is based on molecular weight of proteins. The second-dimension capillary contained a TRIS–CHES–SDS buffer for micellar electrokinetic capillary chromatography. After a 61-s preliminary separation, fractions from the first-dimension capillary were successively transferred to the second-dimension capillary, where they further separated by MECC. The two-dimensional separation required 60 min. 相似文献