全文获取类型
收费全文 | 496篇 |
免费 | 8篇 |
国内免费 | 2篇 |
专业分类
化学 | 422篇 |
晶体学 | 13篇 |
力学 | 3篇 |
数学 | 10篇 |
物理学 | 58篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 10篇 |
2019年 | 9篇 |
2018年 | 2篇 |
2017年 | 3篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 23篇 |
2012年 | 30篇 |
2011年 | 32篇 |
2010年 | 26篇 |
2009年 | 13篇 |
2008年 | 37篇 |
2007年 | 33篇 |
2006年 | 31篇 |
2005年 | 31篇 |
2004年 | 28篇 |
2003年 | 22篇 |
2002年 | 22篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有506条查询结果,搜索用时 15 毫秒
61.
Yokoe H Mitsuhashi C Matsuoka Y Yoshimura T Yoshida M Shishido K 《Journal of the American Chemical Society》2011,133(23):8854-8857
Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an α-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization. 相似文献
62.
Much has been done to study the interplay between geometric and energetic effects on the protein folding energy landscape. Numerical techniques such as molecular dynamics simulations are able to maintain a precise geometrical representation of the protein. Analytical approaches, however, often focus on the energetic aspects of folding, including geometrical information only in an average way. Here, we investigate a semi-analytical expression of folding that explicitly includes geometrical effects. We consider a Hamiltonian corresponding to a Gaussian filament with structure-based interactions. The model captures local features of protein folding often averaged over by mean-field theories, for example, loop contact formation and excluded volume. We explore the thermodynamics and folding mechanisms of beta-hairpin and alpha-helical structures as functions of temperature and Q, the fraction of native contacts formed. Excluded volume is shown to be an important component of a protein Hamiltonian, since it both dominates the cooperativity of the folding transition and alters folding mechanisms. Understanding geometrical effects in analytical formulae will help illuminate the consequences of the approximations required for the study of larger proteins. 相似文献
63.
Noriaki Nishiguchi Takafumi Kinuta Yoko Nakano Dr. Takunori Harada Dr. Nobuo Tajima Tomohiro Sato Prof. Dr. Michiya Fujiki Prof. Dr. Reiko Kuroda Prof. Dr. Yoshio Matsubara Dr. Yoshitane Imai 《化学:亚洲杂志》2011,6(4):1092-1098
The solid‐state chiral optical properties of a 4‐(2‐arylethynyl)‐benzoic acid/amine supramolecular organic fluorophore can be controlled by changing the arylethynyl group of the achiral 4‐(2‐arylethynyl)‐benzoic acid component molecule rather than the chirality of the amine component molecule. 相似文献
64.
Anti-allergic effect of the flavonoid myricitrin from Myrica rubra leaf extracts in vitro and in vivo 总被引:1,自引:0,他引:1
Flavonoids are ingested by the general population as anti-oxidant and anti-inflammatory agents. In this study, we investigated the effects of myricitrin, a flavonoid rich in Myrica rubra leaf, upon anti-inflammatory action. Myrica rubra leaf extracts inhibited pro-inflammatory TNFα production in a macrophage cell line, Raw264.7 cells. We observed that the serum IgE levels in the leaf extract-treated DO11.10, a mouse allergy model, were down-regulated. HPLC was performed to demonstrate that M. rubra leaf extracts contain a large amount of myricitrin. We observed an inhibitory effect of HPLC-purified myricitrin on TNFα production in Raw264.7 cells. Thus, myricitrin may be of potential interest in the management of inflammatory conditions. 相似文献
65.
66.
Masanobu Yamamoto Ryoko Maruyama Yoko Murakami Yuki Sakamoto Rei Yamakawa Tetsu Ando 《Analytical and bioanalytical chemistry》2013,405(23):7405-7414
trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C19–C21 chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO2, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes. 相似文献
67.
Yoko Kuwae Nobuo Kushibiki 《Journal of polymer science. Part A, Polymer chemistry》1989,27(12):3969-3975
The microstructure of the polymer formed by the hydrosilation of styrene with poly(hydrogenmethylsiloxane) was studied by 1H- and 13C-NMR spectra. Two modes of addition in hydrosilation were found to occur randomly without the influence of the adjacent monomer unit by statistical analysis of sequence distribution of 29Si-NMR spectrum. 相似文献
68.
69.
Two trans stereoisomers of 3‐methylcyclopentadecanol (=muscol), (1R,3R)‐ 2 and (1S,3S)‐ 2 , were efficiently synthesized from (3RS)‐3‐methylcyclopentadecanone (=muscone; (3RS)‐ 1 ) by a highly stereoselective reduction (Scheme). L‐Selectride® (=lithium tri(sec‐butyl)borohydride) was used, followed by the enantiomer resolution by lipase QLG (Alcaligenes sp.). The cis stereoisomers of muscol, (1S,3R)‐ 2 and (1R,3S)‐ 2 , were obtained by the Mitsunobu inversion of (1R,3R)‐ 2 and (1S,3S)‐ 2 , respectively (Scheme). The absolute configuration of (1R,3R)‐ 2 was determined by X‐ray crystal‐structure analysis of its 3‐nitrophthalic acid monoester, 2‐[(1R,3R)‐3‐methylcyclopentadecyl hydrogen benzene‐1,2‐dicarboxylate ((1R,3R)‐ 3b ), and by oxidation of (1R,3R)‐ 2 to (3R)‐muscone. 相似文献
70.
Shimaoka H Kuramoto H Furukawa J Miura Y Kurogochi M Kita Y Hinou H Shinohara Y Nishimura S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(6):1664-1673
The development of rapid and efficient methods for high-throughput protein glycomics is of growing importance because the glycoform-focused reverse proteomics/genomics strategy will greatly contribute to the discovery of novel biomarkers closely related to cellular development, differentiation, growth, and aging as well as a variety of diseases such as cancers and viral infection. Recently, we communicated that rapid and efficient purification of carbohydrates can be achieved by employing sugar-specific chemical ligation with aminooxy-functionalized polymers, which we termed "glycoblotting" (see S.-I. Nishimura et al., Angew. Chem. 2005, 117, 93-98; Angew. Chem. Int. Ed. 2005, 44, 91-96). The chemoselective blotting of oligosaccharides present in crude biological materials onto synthetic polymers relies on the unique oxime-bond formation between aminooxy group displayed on the supporting materials and aldehyde/ketone group at the reducing terminal of all oligosaccharides, thus enabling highly selective and rapid oligosaccharide purification. Aiming to improve the detection sensitivity of the released oligosaccharides, we introduce here a novel strategy for one-pot solid-phase glycoblotting and probing by transoximization. We found that oligosaccharides captured by the polymer supports via the oxime bond can be released in the presence of excess O-substituted aminooxy derivatives in a weakly acidic condition. The released oligosaccharides could be recovered as newly formed oxime derivatives of the O-substituted aminooxy compound added, thus demonstrating the simultaneous releasing and probing. In addition, we synthesized a novel aminooxy-functionalized monomer, N-[2-[2-(2-tert-butoxycarbonylaminooxyacetylamino-ethoxy)ethoxy]ethyl]-2-methacrylamide, which allows for the large-scale preparation of a versatile polymer characterized by its high stability, high blotting capacity, and easy use. The one-pot protocol allowed to profile 23 kinds of N-glycan chains of human serum glycoproteins. This concept was further applied for the glycopeptides analysis in a crude mixture followed by galactose oxidase treatment to generate free aldehyde group at the non-reducing terminal of oligosaccharide moiety of glycopeptides. Our technique may be implemented in existing biochemistry and molecular diagnostics laboratories because enriched oligosaccharides and glycopeptides by solid-phase transoximization with high-sensitive labeling reagents are widely applicable in a variety of common analytical methods using two-dimensional HPLC, LC/MS, and capillary electrophoresis as well as modern mass spectrometry. 相似文献