全文获取类型
收费全文 | 1846篇 |
免费 | 87篇 |
国内免费 | 7篇 |
专业分类
化学 | 1518篇 |
晶体学 | 17篇 |
力学 | 28篇 |
数学 | 56篇 |
物理学 | 321篇 |
出版年
2023年 | 15篇 |
2022年 | 15篇 |
2021年 | 36篇 |
2020年 | 45篇 |
2019年 | 54篇 |
2018年 | 35篇 |
2017年 | 21篇 |
2016年 | 58篇 |
2015年 | 40篇 |
2014年 | 41篇 |
2013年 | 115篇 |
2012年 | 95篇 |
2011年 | 125篇 |
2010年 | 50篇 |
2009年 | 56篇 |
2008年 | 88篇 |
2007年 | 75篇 |
2006年 | 95篇 |
2005年 | 74篇 |
2004年 | 72篇 |
2003年 | 68篇 |
2002年 | 51篇 |
2001年 | 52篇 |
2000年 | 40篇 |
1999年 | 33篇 |
1998年 | 14篇 |
1997年 | 16篇 |
1996年 | 23篇 |
1994年 | 28篇 |
1993年 | 17篇 |
1992年 | 43篇 |
1991年 | 21篇 |
1990年 | 25篇 |
1989年 | 23篇 |
1988年 | 27篇 |
1987年 | 24篇 |
1986年 | 18篇 |
1985年 | 23篇 |
1984年 | 25篇 |
1983年 | 15篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1979年 | 9篇 |
1977年 | 10篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 8篇 |
1964年 | 9篇 |
1962年 | 7篇 |
1960年 | 7篇 |
排序方式: 共有1940条查询结果,搜索用时 15 毫秒
101.
Akira Hasegawa Kenichi Ito Hideharu Ishida Makoto Kiso 《Journal of carbohydrate chemistry》2013,32(3):353-368
Abstract Four sialyl and sulfo Lex analogs containing glucose in place of N-acetylglucosamine, and a ceramide or 2-(tetradecyl)hexadecyl residue, have been synthesized. Condensation of O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d-glycero-α-d-galacto-2-nonulopyranosylonate)-(2→3)-O-(4-O-acetyl-2,6-diO-benzoyl-β-d-galactopyranosyl)-(1→4)-O-[(2,3,4-tri-O-acetyl-α-L-fucopyranosyl)-(1→3)]-2,4-di-O-benzoyl-α-d-glucopyranosyl trichloroacetimidate (1) with (2S,3R,4E)-2-azido-3-O-benzoyl-4-octadecene-1,3, diol (2) or 2-(tetradecyl)-hexadecyl-1-ol (3) gave the corresponding β-glycosides 4 and 7. Compound 4 was converted into the ganglioside 6 via selective reduction of the azido group, coupling with octadecanoic acid, O-deacylation, and saponification of the methyl ester group. Hydrolysis of the O-acyl groups in 7 followed by saponification of the methyl ester, gave sialyl Lex ganglioside analog 8 containing a branched fatty alkyl residue. On the other hand, glycosylation of O-(4-O-acetyl-2,6-di-O-benzoyl-3-O-levulinyl-β-d-galactopyranosyl)-(1→4)-[O-(2,3,4-tri-O-acetyl-α-L-fucopyranosyl)-(1→3)]-2,6-di-O-benzoyl-α-d-glucopyranosyl trichloroacetimidate (13), prepared from 2-(trimethylsilyl)ethyl O-(2,6-di-O-benzoyl-β-d-galactopyranosyl)-(1→4)-O-[(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-(1→3)]-2,6-di-O-benzoyl-β-d-glucopyranoside (9) via selective 3-O-levulinylation, acetylation, removal of the 2-(trimethylsilyl)ethyl group, with 2 or 3, gave the desired β-glycosides 14 and 19. Selective reduction of the axido group in 14 followed by coupling with octadecanoic acid gave the ceramide derivative 16. Removal of the levulinyl group in 16 and 19, treatment with sulfur trioxide pyridine complex and subsequent hydrolysis of the protecting groups yielded the corresponding sulfo Lex analogs 18 and 21. 相似文献
102.
Akihiko Kameyama Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(5):799-804
Abstract Sialoglycoconjugates such as glycoproteins and glycolipids are present as components of cell memberanes and play important roles1,2 in biological systems. Sialyl neolactotetrasyl ceramide (IV3NeuAcnLc4Cer), a complex type of ganglioside, was isolated as the major ganglioside of human erythrocytes3 and was shown to be a receptor of that this glycolipid induces granulocytic differentiation of human premyelocytic leukemia cell. 相似文献
103.
Xingzhong Guo Wenyan Li Hui Yang Kazuyoshi Kanamori Yang Zhu Kazuki Nakanishi 《Journal of Sol-Gel Science and Technology》2013,67(2):406-413
An in situ two-step processing using an initial acid catalysis step accompanied by an epoxide-mediated condensation step in the presence of ammonium chloride (NH4Cl) is reported, and macroporous cocontinuous methylsilsesquioxane (MSQ) monoliths have been successfully prepared by this processing. We explain the hydrolysis, gelation behavior and phase separation of MTMS(methyltrimethoxysilane)-MeOH(methanol)-HCl-PO(propylene oxide) system and the in situ effect of NH4Cl, and examine the macroporous morphology and pore structures of MSQ monoliths obtained under different conditions. Macroporous MSQ monolith under optimized conditions possesses a narrow macropore size distribution between 3 to 10 μm, surface area as high as 366 m2·g?1 and minimal shrinkage of only 1 %. 相似文献
104.
Wangdong Zeng Dr. Masatoshi Ishida Sangsu Lee Young Mo Sung Dr. Zebing Zeng Yong Ni Prof. Chunyan Chi Prof. Dongho Kim Prof. Jishan Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16814-16824
A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λmax=955 nm, ε=45400 M ?1 cm?1) and a large two‐photon absorption (TPA) cross‐section (σ(2)max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore. 相似文献
105.
Application of plug–plug technique to ACE experiments for discovery of peptides binding to a larger target protein: A model study of calmodulin‐binding fragments selected from a digested mixture of reduced BSA 下载免费PDF全文
Kazuki Saito Mamiko Nakato Takaaki Mizuguchi Shinji Wada Hiromasa Uchimura Hiroshi Kataoka Shigeyuki Yokoyama Hiroshi Hirota Yoshiaki Kiso 《Electrophoresis》2014,35(6):846-854
To discover peptide ligands that bind to a target protein with a higher molecular mass, a concise screening methodology has been established, by applying a “plug–plug” technique to ACE experiments. Exploratory experiments using three mixed peptides, mastoparan‐X, β‐endorphin, and oxytocin, as candidates for calmodulin‐binding ligands, revealed that the technique not only reduces the consumption of the protein sample, but also increases the flexibility of the experimental conditions, by allowing the use of MS detection in the ACE experiments. With the plug–plug technique, the ACE–MS screening methodology successfully selected calmodulin‐binding peptides from a random library with diverse constituents, such as protease digests of BSA. Three peptides with Kd values between 8–147 μM for calmodulin were obtained from a Glu‐C endoprotease digest of reduced BSA, although the digest showed more than 70 peaks in its ACE–MS electropherogram. The method established here will be quite useful for the screening of peptide ligands, which have only low affinities due to their flexible chain structures but could potentially provide primary information for designing inhibitors against the target protein. 相似文献
106.
Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface
Yuta Ohtani Yohei Ishida Yuka Ando Hiroshi Tachibana Tetsuya Shimada Shinsuke Takagi 《Tetrahedron letters》2014
Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm−2). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity. 相似文献
107.
Hitoshi Tamiaki Shun Koizumi Kazuki Tsuji Yusuke Kinoshita Tomohiro Miyatake 《Tetrahedron letters》2014
Chlorophyll-a derivatives possessing an un/mono/disubstituted methylene moiety at the 131-position were prepared by (un)substituted methylation of the 13-carbonyl group and successive dehydration. Substitution of the 131-oxo to the methylene group slightly blue-shifted electronic absorption and emission bands in a solution and decreased chemical stability to give an oxidation product cleaved at the E-ring. Further mono/disubstitution at the methylene terminal increased wavelengths of absorption and emission maxima as well as oxidative tolerance. 相似文献
108.
Guangxian Su Dr. Qizhao Li Dr. Masatoshi Ishida Dr. Chengjie Li Dr. Feng Sha Prof. Dr. Xin-Yan Wu Lu Wang Dr. Glib Baryshnikov Prof. Dr. Dawei Li Prof. Dr. Hans Ågren Prof. Dr. Hiroyuki Furuta Prof. Dr. Yongshu Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1553-1557
An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring ( 1 ) was synthesized. PdII and BIII coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3 . Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the PdII-coordinating phenoxy group to afford 4 . Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5 . Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3-Ag and 5-Ag , respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination. 相似文献
109.
Koji Yamamoto Kazuki Higuchi Masahiro Ogawa Hiromitsu Sogawa Shigeki Kuwata Yoshihiro Hayashi Susumu Kawauchi Toshikazu Takata 《化学:亚洲杂志》2020,15(3):356-359
We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes. 相似文献
110.
Ashish Kaul Raviprasad Kuthethur Yoshiyuki Ishida Keiji Terao Renu Wadhwa Sunil C. Kaul 《Molecules (Basel, Switzerland)》2022,27(1)
Propolis, also known as bee-glue, is a resinous substance produced by honeybees from materials collected from plants they visit. It contains mixtures of wax and bee enzymes and is used by bees as a building material in their hives and by humans for different purposes in traditional healthcare practices. Although the composition of propolis has been shown to depend on its geographic location, climatic zone, and local flora; two largely studied types of propolis: (i) New Zealand and (ii) Brazilian green propolis have been shown to possess Caffeic Acid Phenethyl Ester (CAPE) and Artepillin C (ARC) as the main bioactive constituents, respectively. We have earlier reported that CAPE and ARC possess anticancer activities, mediated by abrogation of mortalin-p53 complex and reactivation of p53 tumor suppressor function. Like CAPE, Artepillin C (ARC) and the supercritical extract of green propolis (GPSE) showed potent anticancer activity. In this study, we recruited low doses of GPSE and ARC (that did not affect either cancer cell proliferation or migration) to investigate their antistress potential using in vitro cell based assays. We report that both GPSE and ARC have the capability to disaggregate metal- and heat-induced aggregated proteins. Metal-induced aggregation of GFP was reduced by fourfold in GPSE- as well as ARC-treated cells. Similarly, whereas heat-induced misfolding of luciferase protein showed 80% loss of activity, the cells treated with either GPSE or ARC showed 60–80% recovery. Furthermore, we demonstrate their pro-hypoxia (marked by the upregulation of HIF-1α) and neuro-differentiation (marked by differentiation morphology and upregulation of expression of GFAP, β-tubulin III, and MAP2). Both GPSE and ARC also offered significant protection against oxidative stress and, hence, may be useful in the treatment of old age-related brain pathologies. 相似文献