全文获取类型
收费全文 | 1008篇 |
免费 | 6篇 |
国内免费 | 8篇 |
专业分类
化学 | 692篇 |
晶体学 | 13篇 |
力学 | 11篇 |
数学 | 50篇 |
物理学 | 256篇 |
出版年
2022年 | 4篇 |
2020年 | 4篇 |
2019年 | 10篇 |
2018年 | 12篇 |
2017年 | 8篇 |
2016年 | 7篇 |
2015年 | 8篇 |
2014年 | 18篇 |
2013年 | 39篇 |
2012年 | 33篇 |
2011年 | 60篇 |
2010年 | 30篇 |
2009年 | 26篇 |
2008年 | 63篇 |
2007年 | 51篇 |
2006年 | 59篇 |
2005年 | 59篇 |
2004年 | 49篇 |
2003年 | 39篇 |
2002年 | 50篇 |
2001年 | 30篇 |
2000年 | 19篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 14篇 |
1994年 | 19篇 |
1993年 | 15篇 |
1992年 | 19篇 |
1991年 | 13篇 |
1990年 | 14篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1986年 | 19篇 |
1985年 | 19篇 |
1984年 | 14篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 19篇 |
1980年 | 13篇 |
1979年 | 8篇 |
1978年 | 8篇 |
1977年 | 13篇 |
1976年 | 11篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 11篇 |
1972年 | 4篇 |
排序方式: 共有1022条查询结果,搜索用时 0 毫秒
51.
Yamashita M Yamamoto Y Akiba KY Hashizume D Iwasaki F Takagi N Nagase S 《Journal of the American Chemical Society》2005,127(12):4354-4371
Pentacoordinate and tetracoordinate carbon and boron compounds (27, 38, 50-52, 56-61) bearing an anthracene skeleton with two oxygen or nitrogen atoms at the 1,8-positions were synthesized by the use of four newly synthesized tridentate ligand precursors. Several carbon and boron compounds were characterized by X-ray crystallographic analysis, showing that compounds 27, 56-59 bearing an oxygen-donating anthracene skeleton had a trigonal bipyramidal (TBP) pentacoordinate structure with relatively long apical distances (ca. 2.38-2.46 A). Despite the relatively long apical distances, DFT calculation of carbon species 27 and boron species 56 and experimental accurate X-ray electron density distribution analysis of 56 supported the existence of the apical hypervalent bond even though the nature of the hypervalent interaction between the central carbon (or boron) and the donating oxygen atom was relatively weak and ionic. On the other hand, X-ray analysis of compounds 50-52 bearing a nitrogen-donating anthracene skeleton showed unsymmetrical tetracoordinate carbon or boron atom with coordination by only one of the two nitrogen-donating groups. It is interesting to note that, with an oxygen-donating skeleton, the compound 61 having two chlorine atoms on the central boron atom showed a tetracoordinate structure, although the corresponding compound 60 with two fluorine atoms showed a pentacoordinate structure. The B-O distances (av 2.29 A) in 60 were relatively short in comparison with those (av 2.44 A) in 59 having two methoxy groups on the central boron atom, indicating that the B-O interaction became stronger due to the electron-withdrawing nature of the fluorine atoms. 相似文献
52.
Tong Z Takagi S Tachibana H Takagi K Inoue H 《The journal of physical chemistry. B》2005,109(46):21612-21617
A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17).3H(2)O that possesses both (1) optical transparency and (2) ion-exchangeability under ambient conditions without calcination at high temperature. An optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film, a photoresponsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV(2+)-K(4)Nb(6)O(17) as a precursor. The optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin films have been characterized by X-ray diffraction, SEM, AFM, IR, and UV spectroscopies, as well as elemental analysis. The electrochemical behavior of the ITO/Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film electrode was studied; it also exhibits swift photoresponse in the visible region. 相似文献
53.
Tsukahara M Nishino T Furuhashi I Inoue H Sato T Matsumoto H 《Chemical & pharmaceutical bulletin》2005,53(9):1103-1110
Olean-11,13(18)-dien-3beta,30-diol dihemiphthalate (3), which was derived from glycyrrhetinic acid (GA), has been reported to produce a potent of anti-inflammatory effect in in vivo assays. Using 3 as a lead compound, we attempted to synthesize some modified compounds which varied in the following; i) the position of a carboxyl group in the phthalate moiety, ii) the number of carboxyls attached to the benzoyl group, iii) conversion of benzene ring to another ring system, iv) the linkage form between the benzene ring and oleanene skeleton at position 3 and/or 30. These were screened for their inhibitory activity against interleukin-1 beta (IL-1 beta)-induced prostaglandin E(2) (PGE(2)) production in normal human dermal fibroblasts (NHDF). Although conversion of the ortho-carboxyl group of 3 into the meta-position or the para-position led to an increase in inhibitory activity, the elimination or increase of the carboxyl group resulted in loss of the inhibitory activity. Conversion of the ester bond to the amide bond at position 3 and/or 30 of 3 did not contribute to a significant increase in inhibitory activity. On the other hand, among the derivatives possessing an anthranilic acid moiety at position 30 of 3beta-O-acetyl-olean-11,13(18)-dien-30-oic acid (20), 3beta-hydroxy-30-nor-olean-11,13(18)-dien-20 beta-[N-(2-carboxyphenyl)]carboxamide (30) showed the most potent inhibitory activity (IC(50) 1.0 microM) in this series. 相似文献
54.
Shibata T Fujimoto T Yokota K Takagi K 《Journal of the American Chemical Society》2004,126(27):8382-8383
An asymmetric [2+2+2] cycloaddition of an alpha,omega-diyne, possessing ortho-substituted aryl groups on its terminus, and a monoalkyne with oxygen functionalities gave various axially chiral teraryl compounds. The coupling proceeded with extremely high enantio- (>99.5% ee) and diastereoselectivities (dl/meso = >95/5) when catalyzed by an iridium-chiral phosphine complex. As the products were readily transformed into diol compounds by deprotection without racemization, the present procedure provides access to a new chiral pool of diol compounds with C2 symmetry. 相似文献
55.
[reaction: see text] Reaction of gamma-p-toluenesulfonyl-alpha,beta-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords alpha,beta-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions. 相似文献
56.
Hirofumi Kuroda Emi Hanaki Hironori Izawa Michiko Kano Hiromi Itahashi 《Tetrahedron》2004,60(8):1913-1920
α-Vinylfurans were obtained by phosphine-initiated cyclization of various enynes bearing a carbonyl group at the ene end in the presence of various aldehydes, in moderate to high yields. The reaction may consist of 1,6-addition of phosphine to the enynes, ring closure, and Wittig reaction between the ylid resulting from cyclization and an aldehyde. Thus, various aldehydes were able to be used in the reaction. The reaction was influenced greatly by the substituents at the acetylene position (R1) and the α-position of the carbonyl group (R3). 相似文献
57.
Michiko Iwamura Yuka Gotoh Tomoyuki Hashimoto Reiko Sakurai 《Tetrahedron letters》2005,46(37):6275-6277
Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions. 相似文献
58.
M. F. Hussain M. Katyal B. K. Puri Y. Takagi 《International journal of environmental analytical chemistry》2013,93(4):525-531
Abstract A sensitive method has been developed for the direct atomic absorption spectrometric determination of zinc, antimony and lead after coprecipitation of their trifluoroethylxanthates onto microcrystalline naphthalene. The metal xanthates are quantitatively coprecipitated over the pH ranges: Zn, 5.9–8.4; Sb, 4.0–6.0 and Pb, 4.0–11.0. The solid mass consisting of the metal complex and naphthalene is dissolved in DMF. This solution is aspirated into an air-acetylene flame at 213.9, 217.6 and 217.0nm for Zn, Sb and Pb, respectively. Beer's law is obeyed in the concentration range 2–50, 3–90 and 5–60 μg of Zn, Sb and Pb, respectively in 10ml of the final DMF solution. RSDs are at the ± (0.5–0.6)% level (n=10). The concentration for 1% absorption is 0.019, 0.035 and 0.060μg/ml for Zn, Sb and Pb, respectively. The method is suitable for the preconcentration of the metals from a larger volume of the aqueous phase, and has been employed for their determination in standard reference materials. It may be employed for the simultaneous determination of Zn, Pb and Sb in a solution by pH control. 相似文献
59.
Mukhopadhyay I Duan YB Wu XT Takagi K 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,(1):19-28
In this work, we have extended our previous analysis of the Hamiltonian of 13C substituted methanol to include a large number of spectral lines involving the second excited torsional state using an improved model. The data set consisted of 2529 Fourier transform and microwave transitions with the rotational angular momentum J < or = 10, K < or = 6 and n < or = 2 (with 336 MW lines). The data set was fitted with the new Hamiltonian model to derive the molecular parameters. The results indicate that the model developed for the other methanol species (CH3OH, CH3(18)OH and CH3OD) is also valid for the C-13 substituted species. The results will allow the energy levels of the molecule to be calculated for higher torsional levels above the internal rotational barrier with improved precision and allow the analysis to be carried out for more excited torsional states. 相似文献