全文获取类型
收费全文 | 17359篇 |
免费 | 2781篇 |
国内免费 | 1934篇 |
专业分类
化学 | 12595篇 |
晶体学 | 186篇 |
力学 | 1193篇 |
综合类 | 136篇 |
数学 | 2025篇 |
物理学 | 5939篇 |
出版年
2024年 | 55篇 |
2023年 | 334篇 |
2022年 | 543篇 |
2021年 | 577篇 |
2020年 | 632篇 |
2019年 | 664篇 |
2018年 | 531篇 |
2017年 | 540篇 |
2016年 | 766篇 |
2015年 | 765篇 |
2014年 | 951篇 |
2013年 | 1172篇 |
2012年 | 1529篇 |
2011年 | 1545篇 |
2010年 | 1055篇 |
2009年 | 936篇 |
2008年 | 1090篇 |
2007年 | 981篇 |
2006年 | 983篇 |
2005年 | 794篇 |
2004年 | 603篇 |
2003年 | 548篇 |
2002年 | 545篇 |
2001年 | 460篇 |
2000年 | 344篇 |
1999年 | 363篇 |
1998年 | 288篇 |
1997年 | 270篇 |
1996年 | 297篇 |
1995年 | 234篇 |
1994年 | 206篇 |
1993年 | 160篇 |
1992年 | 169篇 |
1991年 | 173篇 |
1990年 | 128篇 |
1989年 | 123篇 |
1988年 | 81篇 |
1987年 | 70篇 |
1986年 | 80篇 |
1985年 | 60篇 |
1984年 | 54篇 |
1983年 | 44篇 |
1982年 | 32篇 |
1981年 | 31篇 |
1980年 | 29篇 |
1978年 | 24篇 |
1977年 | 25篇 |
1976年 | 23篇 |
1974年 | 20篇 |
1973年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
851.
The organocatalytic sulfenylation of α-nitroesters mediated by diaryl-l-prolinols was developed. A range of α-sulfenylated α-nitroesters were obtained in good yields with moderate to good enantioselectivities. 相似文献
852.
Qiu‐Yan Chen Xian Cheng Tao Wang Zi‐Hao Yu Chong Zhang Shu‐Kun Lin Hao‐Hong Li Zhi‐Rong Chen 《无机化学与普通化学杂志》2014,640(2):439-443
A new low‐dimensional benzyl viologen/iodoargentate hybrid, [(BV)2(Ag5I9)]n ( 1 ) (BV2+ = benzyl viologen) was prepared. In 1 , (Ag6I9)n2– chain exhibits a new type of one‐dimensional chain constructed from vertex‐sharing of Ag5I10 units, and its two‐dimensional layer structure was constructed from C–H ··· I hydrogen bonds. Strong luminescence at 404 nm can be detected in 1 . DFT calculation suggests that 1 displays a reduced bandgap, which is led by a more dispersed LUMO band of BV2+ compared with MV2+ in [MV(Ag2I4)]n. 相似文献
853.
Jayachandran Jayakumar Kanniyappan Parthasarathy Yi‐Hsiang Chen Tai‐Hua Lee Shih‐Ching Chuang Chien‐Hong Cheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(37):10047-10050
A new method for the synthesis of highly substituted naphthyridine‐based polyheteroaromatic compounds in high yields proceeds through rhodium(III)‐catalyzed multiple C H bond cleavage and C C and C N bond formation in a one‐pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π‐conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation‐assisted ortho C H activation, alkyne insertion, and reductive elimination, is proposed for this transformation. 相似文献
854.
Wenjuan Cheng Lu‐Tao Weng Yongjie Li Arthur Lau Chak Chan Chi‐Ming Chan 《Surface and interface analysis : SIA》2014,46(7):480-488
Size‐segregated particles were collected with a ten‐stage micro‐orifice uniform deposit impactor from a busy walkway in a downtown area of Hong Kong. The surface chemical compositions of aerosol samples from each stage were analyzed using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) operated in the static mode. The ToF‐SIMS spectra of particles from stage 2 (5.6–10 µm), stage 6 (0.56–1 µm), and stage 10 (0.056–0.1 µm) were compared, and the positive ion spectra from stage 2 to stage 10 were analyzed with principal component analysis (PCA). Both spectral analysis and PCA results show that the coarse‐mode particles were associated with inorganic ions, while the fine particles were associated with organic ions. PCA results further show that the particle surface compositions were size dependent. Particles from the same mode exhibited more similar surface features. Particles from stage 2 (5.6–10 µm), stage 6 (0.56–1 µm), and stage 10 (0.056–0.1 µm) were further selected as representatives of the three modes, and the chemical compositions of these modes of particles were examined using ToF‐SIMS imaging and depth profiling. The results reveal a non‐uniform chemical distribution from the outer to the inner layer of the particles. The coarse‐mode particles were shown to contain inorganic salts beneath the organics surface. The accumulation‐mode particles contained sulfate, nitrate, ammonium salts, and silicate in the regions below a thick surface layer of organic species. The nucleation‐mode particles consisted mainly of soot particles with a surface coated with sulfate, hydrocarbons, and, possibly, fullerenic carbon. The study demonstrated the capability of ToF‐SIMS depth profiling and imaging in characterizing both the surface and the region beneath the surface of aerosol particles. It also revealed the complex heterogeneity of chemical composition in size and depth distributions of atmospheric particles. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
855.
Recombination fractions between forensic STRs can be extrapolated from the International HapMap Project, but the concordance between recombination fractions predicated from genetic maps and derived from observation of STR transmissions in families is still ambiguous for autosomal STRs because of limited family studies. Therefore, the main goal of this study is to compare recombination fractions estimated by pedigree analysis with those derived from HapMap phase SNP data. Genotypes of nine autosomal STR pairs (TPOX‐D2S1772, D5S818‐CSF1PO, D7S3048‐D7S820, D8S1132‐D8S1179, TH01‐D11S2368, vWA‐D12S391, D13S325‐D13S317, D18S51‐D18S1364, and D21S11‐PentaD) from 207 two‐generation families with two to five children (the number of families with five, four, three, and two children was 2, 3, 20, and 182, respectively) were used to analyze the recombination. The linkage analysis showed that significant linkage was observed at six STR pairs (D5S818‐CSF1PO, D8S1132‐D8S1179, TH01‐D11S2368, vWA‐D12S391, D13S325‐D13S317, and D18S51‐D18S1364) with genetic distances <36.22 cM in HapMap. Their recombination fractions calculated from family data were very close to those derived from HapMap. However, three STR pairs of TPOX‐D2S1772, D7S3048‐D7S820, and D21S11‐PentaD showed no significant linkage with genetic distances from 43.38 to 91.49 cM. Our results indicate that recombination fractions extrapolated from HapMap can provide a substitute if empirical data are unavailable for the linkage STR pair with a genetic distance spanned <36.22 cM. 相似文献
856.
A simple fabrication method for tapered capillary tip and its applications in high‐speed CE and ESI‐MS
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yong‐Qiang Cheng Yuan Su Xiao‐Xia Fang Jian‐Zhang Pan Qun Fang 《Electrophoresis》2014,35(10):1484-1488
Fabrication of capillaries with tapered tips is an important technique that is required in many analytical chemistry areas, such as ESI‐MS, CE, electrochemical analysis, and microinjection. This paper describes a simple and effective grinding‐based fabrication method for capillaries with tapered tips. A novel grinding mode utilizing the combination of rotation and precession of an elastic capillary was developed, which significantly improved the controllability to the grinding process as well as the capillary tip shape. The capillary was fabricated by fixing it in an electric drill installed perpendicularly, and grind the capillary tip rotated around its own axis as well as the drill axis on sandpapers. Compared with conventional fabrication techniques for capillary tips, the present method is easy to control the capillary tip shape in routine laboratories without the requirement of expensive equipments or poisonous reagent (e.g. hydrofluoric acid (HF) solution). Various capillaries with different tip diameters and tip taper angles could be fabricated using the present method with good controllability and reproducibility. These capillaries were applied in high‐speed CE and ESI‐MS analysis to demonstrate the feasibility and potential of this fabrication method. 相似文献
857.
Sheng-Yin Zhao Bao-Shuo Liu Jing Huang Shao-Hua Cheng Yun-xia Deng Zhi-Yu Shao 《合成通讯》2014,44(14):2066-2075
Thermal-induced dimerization cyclization of ethyl N-(styrylcarbamoyl)acetate derivatives has been investigated, leading to 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives with good yields in diphenyl ether on 200–210 °C. Ethyl N-(styrylcarbamoyl)acetate derivatives readily provided the intermolecular cyclization products 4-hydroxy-2(1H)-pyridone-3-carboxylates on reflux in xylene. In addition, several related 3-acetyl-4-hydroxy-5-phenylpyridin-2(1H)-ones have been prepared. It provided an efficient preparation of 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives. 相似文献
858.
Jian-Jun Tang Li Zhang Li-Ping Jiang Lei Di Yong-Ming Yan Zheng-Chao Tu Cui-Ping Yang Zhi-Li Zuo Bo Hou Hou-Lin Xia Yong-Bin Chen Yong-Xian Cheng 《Tetrahedron》2014
Polyrhachis dives is consumed as an insect food in some regions of China. In this study, new dopamine derivatives, (+)-polyrhadopamine A (1a) and (−)-polyrhadopamine A (1b), (+)-polyrhadopamine B (2a) and (−)-polyrhadopamine B (2b), and polyrhadopamines C–E (3–5), were isolated from this species. The structures and stereochemistry of these substances were assigned by using spectroscopic and computational methods. Compounds 1a, 1b, 2a, and 2b are dimeric N-acetyldopamine derivatives, 3 is a dopamine analog containing an unusual sulfone group, and 4 and 5 possess a rare benzo[d]thiazole moiety. The functions of these substances as ROCK1/2 inhibitors, neural stem cell (NSCs) proliferation stimulators, immunosuppressive, and anti-inflammatory agents were determined. 相似文献
859.
Xiu-Jiang Du Zhi-Peng WangYan-Ling Hou Cheng ZhangZheng-Ming Li Wei-Guang Zhao 《Tetrahedron letters》2014
A new method has been developed for the Michael addition of nitrogen- and carbon-containing nucleophiles to cyclic enones. Using this conjugate addition reaction, a variety of different nucleophiles can react with a range of cyclic enones in the presence of p-toluenesulfonic acid under solvent-free ultrasound irradiation conditions affording the corresponding C–N or C–C adducts in good to excellent yields. Comparatively, performing the reaction under ultrasound irradiation gives higher yields, is more efficient and environmentally benign than performing it at high pressure. 相似文献
860.
Xing-Wei Yang Xu-Jie Qin Yun-Li Zhao Paul K. Lunga Xiao-Nian Li Shi-Zhi Jiang Gui-Guang Cheng Ya-Ping Liu Xiao-Dong Luo 《Tetrahedron letters》2014
Three novel ring-fused monoterpenoid indole alkaloids, alstolactines A–C (1–3), were isolated from the long-term stored leaves of Alstonia scholaris. Their structures were identified on the basis of extensive spectroscopic data and X-ray diffractions. Moreover, the absolute configurations of these related structures were indicated by the crystal X-ray diffractions (Mo Kα) of 1a, a chlorinated derivative of 1. 相似文献