全文获取类型
收费全文 | 285篇 |
免费 | 2篇 |
专业分类
化学 | 186篇 |
晶体学 | 7篇 |
力学 | 2篇 |
数学 | 5篇 |
物理学 | 87篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2016年 | 4篇 |
2015年 | 1篇 |
2014年 | 3篇 |
2013年 | 14篇 |
2012年 | 13篇 |
2011年 | 22篇 |
2010年 | 14篇 |
2009年 | 4篇 |
2008年 | 23篇 |
2007年 | 17篇 |
2006年 | 24篇 |
2005年 | 12篇 |
2004年 | 15篇 |
2003年 | 4篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有287条查询结果,搜索用时 9 毫秒
11.
Kosuke Yasui Miharu Kamitani Mamoru Tobisu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14295-14299
Concerted nucleophilic aromatic substitution (CSNAr) has emerged as a powerful mechanistic manifold, in which nucleophilic aromatic substitution can proceed in one step without the need to form a Meisenheimer intermediate. However, all of the CSNAr reactions reported thus far require a stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization of acrylamides that contain a 2‐fluorophenyl group on the nitrogen through a CSNAr reaction. By using this catalytic method, it is possible to synthesize an array of quinolin‐2‐one derivatives, which are common structural motifs in pharmaceuticals and organic materials. DFT calculations unambiguously revealed that this reaction proceeds through the concerted nucleophilic aromatic substitution of aryl fluorides, in which a stereoelectronic σ (Cipso‐Cβ)→ σ*(Cipso‐F) interaction critically contributes to the stabilization of the transition state for the cyclization. 相似文献
12.
Fujiko Iwasaki Hideyuki Nishiyama Noriko Manabe Masanori Yasui Noboru Matsumura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):429-430
Abstract Novel metal-carbene complexes (4) with a metallapentalene framework have been obtained from hypervalent diazadiselenathiapentalenes (3) by treating with Pt(PPh3)4, Pd(PPh3)4 and RhCl(PPh3)3. X-Ray investigations revealed that the central hypervalent sulfur atom in 3 was substituted by a metal atom to form M-Se bonds in the resultant metallapentalene framework. 相似文献
13.
Noboru Matsumura Motoyuki Kusamiya Hiroo Inoue Masanori Yasui Fujiko Iwasaki 《Journal of heterocyclic chemistry》1995,32(4):1269-1275
1,3-Bis(p-substituted-phenylthiocarbamoyl)-2-imidazolidinethiones 3a-f reacted with bromine to give trithiadiazapentalene derivatives 5a-f , bearing the exocyclic C-N double bonds, in moderate yields. The molecular structure of 5b was elucidated by the X-ray crystallographic analysis. The treatment of 5b-f with hydrochloric acid gave the ring-opening products, 1,3-bis(p-substituted-phenylthiocarbamoyl)-2-imidazo-lidinones 9b-f , accompanied by the production of elemental sulfur. Reduction of 5b , 5d , and 5e with sodium borohydride gave the ring-opening compounds, 1,3-bis(p-substituted-phenylthiocarbamoyl)-2-imidazolidines 13b , 13d , and 13e respectively. 相似文献
14.
Watanabe J Oki T Takebayashi J Yamasaki K Takano-Ishikawa Y Hino A Yasui A 《Analytical sciences》2012,28(2):159-165
Hydrophilic oxygen radical absorbance capacity (H-ORAC) is a method for evaluating antioxidant capacities of solutions of hydrophilic compounds. In this study, we improved the original method for H-ORAC determination, and evaluated the precision of the two improved methods (methods A and B) by interlaboratory studies using 5 antioxidant solutions and 5 food extracts as test samples. An interlaboratory study of method A, in accordance with the harmonized protocol, demonstrated satisfactory performance (intermediate precision relative standard deviations (RSD(int)) ranging from 4.6 to 18.8%; the reproducibility relative standard deviations (RSD(R)) ranging from 7.0 to 21.1%, and the HorRat values ranging from 0.40 to 1.93). However, methodological problems remained, and a further improved method, method B, was thus developed. An interlaboratory study of method B by 5 participating laboratories showed better intermediate precision and reproducibility (RSD(int) and RSD(R) ranging from 1.8 to 9.4%, and from 4.4 to 13.8%, respectively), and all HorRat values for the test samples were less than 1.3, suggesting good performance for the H-ORAC measurement. 相似文献
15.
16.
Fujiko Iwasaki Seui Kakuma Satoshi Yoshida Shin Murata Masanori Yasui 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):515-516
Abstract The deformation electron-density distributions of 6a-thia-1,3,4,6-tetraazapentalene derivatives (I, II) and bis(phenylthio)dibenzothiophene (III) were investigated by the X-ray diffraction method. For I and II, a structure around the hypervalent S-N bonds is a trigonal bipyramid with equatorial sp2 hybrid of S-C bond and lone-pair electrons and apical polarized S-N bonds. In 111 lone-pair electron densities are observed perpendicular to the thiophene ring and the C-S-C sulfide planes. 相似文献
17.
Nanosized TiO2 supported on activated alumina was prepared using a sonochemical method. To prepare this supported material, direct immersion horn and cup horn ultrasonic systems were used. The efficiency of the sonochemical coating process was determined by UV photodecolourisation of the aqueous methyl orange solution. It was found that TiO2 supported on activated alumina prepared by the sonochemical method gave the maximum decolourisation efficiency. In that method itself, direct immersion horn gave a higher photodecolourisation activity as compared to the cup horn. The obtained results suggest that the direct immersion horn results in uniform, as well as a maximum number of TiO2 particles to be adsorbed on an activated alumina surface. 相似文献
18.
Takao K Yasui H Yamamoto S Sasaki D Kawasaki S Watanabe G Tadano K 《The Journal of organic chemistry》2004,69(25):8789-8795
The total syntheses of (+)-mycoepoxydiene and (-)-1893A have been completed. The present synthetic strategy features the use of one-pot ring-opening/cross metathesis (ROM/CM) followed by a ring-closing metathesis (RCM) reaction, allowing for the concise construction of the 9-oxabicyclo[4.2.1]nona-2,4-diene framework from a 7-oxabicyclo[2.2.1]hept-2-ene derivative and 1,3-butadiene. The sequential metathesis product was converted into (+)-mycoepoxydiene through the oxidative rearrangement of a furfuryl alcohol to a pyranone, thereby establishing its absolute stereochemistry. From the common intermediate, a structurally related natural product (-)-1893A was also synthesized via the vinylogous aldol reaction. 相似文献
19.
20.
Inumaru K Kasahara T Yasui M Yamanaka S 《Chemical communications (Cambridge, England)》2005,(16):2131-2133
Well-crystallised TiO2 particles (P-25, 20-30 nm in diameter) were directly incorporated into surfactant-templated mesoporous silica particles (pore diameter: 2.7 nm), and the composite material with a high TiO2 content (60 wt%) showed molecular selective and enhanced photocatalysis for decomposition of 4-nonylphenol. 相似文献