全文获取类型
收费全文 | 2789篇 |
免费 | 103篇 |
国内免费 | 10篇 |
专业分类
化学 | 2222篇 |
晶体学 | 30篇 |
力学 | 17篇 |
数学 | 92篇 |
物理学 | 541篇 |
出版年
2023年 | 19篇 |
2022年 | 22篇 |
2021年 | 27篇 |
2020年 | 36篇 |
2019年 | 33篇 |
2018年 | 35篇 |
2017年 | 26篇 |
2016年 | 63篇 |
2015年 | 51篇 |
2014年 | 75篇 |
2013年 | 146篇 |
2012年 | 182篇 |
2011年 | 149篇 |
2010年 | 81篇 |
2009年 | 105篇 |
2008年 | 158篇 |
2007年 | 184篇 |
2006年 | 179篇 |
2005年 | 169篇 |
2004年 | 128篇 |
2003年 | 107篇 |
2002年 | 85篇 |
2001年 | 66篇 |
2000年 | 65篇 |
1999年 | 31篇 |
1998年 | 32篇 |
1997年 | 25篇 |
1996年 | 27篇 |
1995年 | 21篇 |
1994年 | 23篇 |
1993年 | 26篇 |
1992年 | 33篇 |
1991年 | 20篇 |
1990年 | 23篇 |
1989年 | 12篇 |
1988年 | 26篇 |
1987年 | 24篇 |
1986年 | 27篇 |
1985年 | 45篇 |
1984年 | 36篇 |
1983年 | 20篇 |
1982年 | 33篇 |
1981年 | 24篇 |
1980年 | 18篇 |
1979年 | 19篇 |
1978年 | 22篇 |
1976年 | 14篇 |
1975年 | 18篇 |
1974年 | 22篇 |
1973年 | 13篇 |
排序方式: 共有2902条查询结果,搜索用时 31 毫秒
81.
Jun Haginaka Chikako Seyama Tokiko Murashima
Hiroya Fujima
Hiroo Wada 《Journal of chromatography. A》1994,660(1-2):275-281The influence of the physical properties of base silica materials and spacer length on chiral separation of enantiomers on ovomucoid (OVM)-bonded materials was investigated. With regard to the pore size of the base silica materials, the 300-Å materials gave higher enantioselectivity, than the 120-Å materials, despite the smaller amounts of bonded OVM proteins. However, higher resolution was obtained with the latter materials. With regard to the spacer length, aminopropyl (AP)-, aminobutyl-, N-(4-aminobutyl)-3-aminopropyl- and N-(6-aminohexyl)-3-aminopropyl-silica gels were activated by N,N′-di-succinimidyl carbonate (DSC) and the proteins were bound. The first two materials showed excellent chiral resolution properties for the solutes tested, and the AP materials gave higher enantioselectivity and resolution. On the other hand, only oxprenolol enantiomers were slightly resolved on the last two materials. Also, AP-silica gels activated by DSC were compared with glycerylpropyl (GP)-silica gels activated by 1,1′-carbonyldiimidazole. The former materials gave higher resolution for acidic and basic solutes despite the lower enantioselectivity, whereas for the unchanged hexobarbital the latter materials gave higher enantioselectivity and almost equal resolution. The above results reveal that the 120-Å base silica gels are more suitable than the 300- Å base silica gels for obtaining larger amounts of bonded OVM proteins and that a less hydrophobic spacer such as an AP group and a hydrophilic spacer such as a GP group are suitable. 相似文献
82.
Masaki Tachibana Motohisa Furusawa Nobutoshi Kiba 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(4):313-329
Extraction of carbazole in heptane was performed at 25±1°C with an aqueous dimethyl sulfoxide (DMSO) medium containing -cyclodextrin (CD) at consecutive concentrations in the range of 0–10 mM. The fluorescence intensity of carbazole remaining in the heptane phase was measured by synchronous scanning fluorimetry. The apparent formation constant (K
f) for a 1:1 carbazole: CD inclusion complex in water-DMSO medium was determined by using a linear plot of the distribution ratio calculated from the fluorescence intensities vs. the -CD concentration. The values thus obtained ranged from 477 M–1 in a 10% v/v DMSO medium to 12.1 M–1 in a 60% v/v medium. Good linear relationships were observed between logK
f and the DMSO concentration ([DMSO]), and also between logK
f and the logarithm of the distribution coefficient (K
d) for carbazole. The formation constant in 100% water was estimated to be approximately 1.0×103 M–1 on the basis of the logK
f vs. [DMSO] and the logK
f vs. logK
d correlations. 相似文献
83.
Hayami S Hashiguchi K Juhász G Ohba M Okawa H Maeda Y Kato K Osaka K Takata M Inoue K 《Inorganic chemistry》2004,43(14):4124-4126
Cobalt(II) compounds [Co(pyterpy)Cl(2)].MeOH (1.(MeOH)) and [Co(pyterpy)Cl(2)].2H(2)O (1.(2H(2)O)) were synthesized. The compound 1.(MeOH) forms the quasi 3-D networks by making pi-pi stacking between the 1-D chains. The methanol molecules from 1.(MeOH) can be removed by heating, and substituted by absorption of water molecules. The MeOH molecules in 1.(MeOH) are removed by heating at 410 K, and they are substituted by water molecules to form 1.(2H(2)O). 1.(2H(2)O) exhibits a S = (3)/(2) (HS) left arrow over right arrow S = (1)/(2) (LS) spin transition with a thermal hysteresis. We have succeeded in constructing a guest dependent 1-D spin-crossover cobalt(II) compound. 相似文献
84.
Akai S Kawashita N Satoh H Wada Y Kakiguchi K Kuriwaki I Kita Y 《Organic letters》2004,6(21):3793-3796
[reaction: see text] The reactions of (phenylsulfinyl)furans or -thiophenes with carbon nucleophiles in the presence of trifluoroacetic anhydride allowed the nucleophilic installation of carbon functional groups on the furan and thiophene nuclei with complete regioselectivity. 相似文献
85.
M. Hashimoto H. Wada T. Omori K. Yoshihara 《Journal of Radioanalytical and Nuclear Chemistry》1991,153(4):283-291
Tc(III)-EDTA complex has been synthesized by the ligand substitution reaction of hexakis-(thiourea) technetium(III) ion with EDTA. The complex exhibits absorption maxima at 368 and 470 nm. The formation reaction proceeds predominantly as follows:
相似文献
86.
A convenient synthetic approach is established to prepare a new class of 1-l-α-amino acid derivatives of phospholene oxides by amination of (±)-1-chloro-2-phospholene-1-oxides with several optically pure l-α-amino acid esters. All compounds obtained as a diastereomeric mixture in good to high yields. The two diastereomers were successfully separated by column chromatography and structurally identified by their spectral analyses. 相似文献
87.
Masao Nohara Masaki Hasegawa Hatsuhiko Harashina Yoichi Iitaka 《Journal of polymer science. Part A, Polymer chemistry》1988,26(10):2695-2704
Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,4 followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer. 相似文献
88.
When milled together with bismuth shot in the presence of allyl halide, aromatic aldehydes readily underwent a Barbier-type allylation to afford the corresponding homoallyl alcohols in good yield. In contrast to the failure in solution reaction, aromatic ketones also underwent allylic carbonyl addition under solvent-free conditions to give the expected tertiary homoallyl alcohols in moderate to good yield. 相似文献
89.
Oxophilic synthetic receptors were designed and synthesized using a porphyrin scaffold, with the aim of constructing a preorganized complementary binding site for phenols and carbohydrates. We pursued three strategies for phenol recognition: (1) Lewis acid/Lewis base combinations serving as a hydrogen bond donor and acceptor for the OH group, (2) Lewis base/pi-pi stacking, targeting both the OH group and the aromatic moiety of phenols, and (3) exchange of the axial hydroxyl ligand on a trivalent and oxophilic metal center of aluminum porphyrin. For the recognition of acidic phenols, the most promising recognition motif was Lewis base/pi-pi stacking, which can bind to phenols with a hydrogen bond and pi-pi stacking interactions. [5-(8-Quinolyl)-10,15,20-triphenylporphyrinato]zinc binds to p-nitrophenol with a binding constant of 540 M(-)(1) in CHCl(3) at 25 degrees C. For carbohydrate recognition, we designed the metalloporphyrin receptor having 8-quinolyl groups and o-carbomethoxymethoxyphenyl groups, where these Lewis basic parts serve as the cooperative hydrogen bonding sites for the hydroxyl groups of glucoside. The receptor binds to beta-octyl glucoside with a binding constant of 7.35 x 10(4) M(-)(1) in CHCl(3) at 15 degrees C, demonstrating importance of formation of a highly ordered hydrogen bonding network between the receptor and the guest. These binding features have significant implications for the rational design of oxophilic artificial receptors. 相似文献
90.
Yasunori Inoue Hiro-o Hamaguchi Kotaro T. Yamamoto Mitsuo Tasumi Masaki Furuya 《Photochemistry and photobiology》1985,42(4):423-427
Abstract— Fluorescence spectra of native rye phytochrome were determined under different light conditions at liquid nitrogen temperature. Fluorescence spectrum of the red-light-absorbing form (Pr) had a major peak at about 685 nm (14 600 cm
|