全文获取类型
收费全文 | 403篇 |
免费 | 35篇 |
国内免费 | 1篇 |
专业分类
化学 | 321篇 |
晶体学 | 6篇 |
力学 | 3篇 |
数学 | 57篇 |
物理学 | 52篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 21篇 |
2019年 | 22篇 |
2018年 | 25篇 |
2017年 | 7篇 |
2016年 | 24篇 |
2015年 | 25篇 |
2014年 | 18篇 |
2013年 | 29篇 |
2012年 | 30篇 |
2011年 | 43篇 |
2010年 | 29篇 |
2009年 | 16篇 |
2008年 | 34篇 |
2007年 | 29篇 |
2006年 | 25篇 |
2005年 | 12篇 |
2004年 | 10篇 |
2003年 | 8篇 |
2002年 | 9篇 |
2001年 | 1篇 |
1996年 | 1篇 |
1994年 | 1篇 |
排序方式: 共有439条查询结果,搜索用时 24 毫秒
161.
A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium‐Doped TiO2 Nanosheet
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Shintaro Ida Kenta Sato Tetsuya Nagata Prof. Hidehisa Hagiwara Prof. Motonori Watanabe Namhoon Kim Prof. Yoshihito Shiota Prof. Michio Koinuma Prof. Sakae Takenaka Prof. Takaaki Sakai Prof. Elif Ertekin Prof. Tatsumi Ishihara 《Angewandte Chemie (International ed. in English)》2018,57(29):9073-9077
The hydrogen evolution reaction using semiconductor photocatalysts has been significantly improved by cocatalyst loading. However, there are still many speculations regarding the actual role of the cocatalyst. Now a photocatalytic hydrogen evolution reaction pathway is reported on a cocatalyst site using TiO2 nanosheets doped with Rh at Ti sites as one‐atom cocatalysts. A hydride species adsorbed on the one‐atom Rh dopant cocatalyst site was confirmed experimentally as the intermediate state for hydrogen evolution, which was consistent with the results of density functional theory (DFT) calculations. In this system, the role of the cocatalyst in photocatalytic hydrogen evolution is related to the withdrawal of photo‐excited electrons and stabilization of the hydride intermediate species; the presence of oxygen vacancies induced by Rh facilitate the withdrawal of electrons and stabilization of the hydride. 相似文献
162.
Undoped Layered Perovskite Oxynitride Li2LaTa2O6N for Photocatalytic CO2 Reduction with Visible Light
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Takayoshi Oshima Tom Ichibha Ken Sinkou Qin Kanemichi Muraoka Dr. Junie Jhon M. Vequizo Keisuke Hibino Ryo Kuriki Dr. Shunsuke Yamashita Prof. Dr. Kenta Hongo Dr. Tomoki Uchiyama Prof. Dr. Kotaro Fujii Dr. Daling Lu Prof. Dr. Ryo Maezono Prof. Dr. Akira Yamakata Prof. Dr. Hideki Kato Dr. Koji Kimoto Prof. Dr. Masatomo Yashima Prof. Dr. Yoshiharu Uchimoto Prof. Dr. Masato Kakihana Prof. Dr. Osamu Ishitani Prof. Dr. Hiroshi Kageyama Prof. Dr. Kazuhiko Maeda 《Angewandte Chemie (International ed. in English)》2018,57(27):8154-8158
Oxynitrides are promising visible‐light‐responsive photocatalysts, but their structures are almost confined with three‐dimensional (3D) structures such as perovskites. A phase‐pure Li2LaTa2O6N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium‐rich oxide precursor. Li2LaTa2O6N exhibited high crystallinity and visible‐light absorption up to 500 nm. As opposed to well‐known 3D oxynitride perovskites, Li2LaTa2O6N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2LaTa2O6N possesses a lower density of mid‐gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride. 相似文献
163.
Kinuta M Kinuta K Yamada H Abe T Yoshida Y Araki K Li SA Otsuka A Nakanishi A Moriyama Y Takei K 《Electrophoresis》2003,24(18):3212-3218
Exposure of the skin to sunlight results in an increase of the content of epidermal trans-urocanic acid, a key metabolite of L-histidine, and also in occurrence of the isomerization of trans-urocanic acid to the cis isomer. S-[2-Carboxy-1-(1H-imidazol-4-yl)ethyl]glutathione (GS(CIE)), an adduct of urocanic acid and glutathione, is a presumed origin of a urinary compound S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]-L-cysteine (Cys(CIE)). The formation of GS(CIE) is stimulated by exposing the skin to sunlight irradiation. In this study we investigated an enzymatic formation of GS(CIE) from glutathione and cis-urocanic acid by incubation with rat liver extract that contained glutathione S-transferase (GST) at high activity. The formation of GS(CIE) was suppressed significantly when a liver extract depleted of GST activity was used. Enzymatic degradation of GS(CIE) with gamma -glutamyl transpeptidase resulted in the formation of N-[S-[2-carboxy-1-(1H-imidazol-4-yl)ethyl]-L-cysteinyl]glycine, a metabolic intermediate between the glutathione adduct and Cys(CIE). A hydrolyzed product of GS(CIE) by HCl was identical with the urinary Cys(CIE). Compounds were analyzed by high-voltage paper electrophoresis, capillary electrophoresis, and fast atom bombardment mass spectrometry. From these results, we suggest that GS(CIE) formed from cis-urocanic acid and glutathione is an origin of the urinary compound Cys(CIE) and that the formation reaction is catalyzed mostly by the action of GST. 相似文献
164.
Palladium (Pd) nanoparticles were prepared using the phase transfer method and coated with alkylamines as stabilizing agents stably dispersed in nonpolar solvents. Spherical Pd nanoparticles with an average diameter of 4 nm and a relatively narrow size distribution were obtained using hexylamine or dodecylamine, and they were successfully incorporated in microemulsion-based gelatin organogel (OG); also, an OG network containing Pd nanoparticles was prepared via drying. For the Mizoroki-Heck cross-coupling reaction of iodobenzene with methyl acrylate in supercritical carbon dioxide, the Pd nanoparticles in the OG network exhibited much higher reactivity than those in powder state. Preparation conditions of OG (e.g., gelatin concentration) affected the apparent reactivity of the supported Pd nanoparticles. The Pd nanoparticles in the OG network with high gelatin concentration were recycled with no appreciable change of reactivity. In contrast, the reactivity of the Pd nanoparticles with low gelatin concentration decreased during recycling. 相似文献
165.
Inside Cover: Detailed Investigation of the Structural,Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano‐Triggered Single‐Crystal‐to‐Single‐Crystal Phase Transitions (Chem. Eur. J. 6/2016)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
166.
Prof. Dr. Masaki Shimizu Kenta Nishimura Rika Hirakawa Dr. Tsuneaki Sakurai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(5):1626-1637
The design and development of organic luminophores that exhibit efficient ultraviolet (UV) fluorescence in the solid state remains underexplored. Here, we report that 1,4-dialkenyl-2,5-dialkoxybenzenes and 1,4-dialkenyl-2,5-disiloxybenzenes act as such UV-emissive fluorophores. The dialkenyldioxybenzenes were readily prepared in three steps from 2,5-dimethoxy-1,4-diacetylbenzene or 2,5-dimethoxy-1,4-diformylbenzene via two to four steps from 1,4-bis(diethoxyphosphonylmethyl)-2,5-dimethoxybenzene. The dialkenyldioxybenzenes emit UV light in solution (λem=350–387 nm) and in the solid state (λem=328–388 nm). In addition, the quantum yields in the solid state were generally higher than those in solution. In particular, the adamantylidene-substituted benzenes fluoresced in the UV region with high quantum yields (Φ=0.37–0.55) in the solid state. Thin films of poly(methyl methacrylate) doped with the adamantylidene-substituted benzenes also exhibited UV emission with good efficiency (Φ=0.27–0.45). Density functional theory calculations revealed that the optical excitation of the dialkenyldimethoxybenzenes involves intramolecular charge-transfer from the ether oxygen atoms to the twisted alkenyl-benzene-alkenyl moiety, whereas the dialkenylbis(triphenylsiloxy)benzenes were optically excited through intramolecular charge-transfer from the oxygen atoms and twisted π-system to the phenyl-Si moieties of each triphenylsilyl group. 相似文献
167.
In the last few decades, development of novel experimental techniques, such as new types of disulfide (SS)-forming reagents and genetic and chemical technologies for synthesizing designed artificial proteins, is opening a new realm of the oxidative folding study where peptides and proteins can be folded under physiologically more relevant conditions. In this review, after a brief overview of the historical and physicochemical background of oxidative protein folding study, recently revealed folding pathways of several representative peptides and proteins are summarized, including those having two, three, or four SS bonds in the native state, as well as those with odd Cys residues or consisting of two peptide chains. Comparison of the updated pathways with those reported in the early years has revealed the flexible nature of the protein folding pathways. The significantly different pathways characterized for hen-egg white lysozyme and bovine milk α-lactalbumin, which belong to the same protein superfamily, suggest that the information of protein folding pathways, not only the native folded structure, is encoded in the amino acid sequence. The application of the flexible pathways of peptides and proteins to the engineering of folded three-dimensional structures is an interesting and important issue in the new realm of the current oxidative protein folding study. 相似文献
168.
Kotatha Ditpon Morishima Kenta Uchida Satoshi Ogino Mayuko Ishikawa Masashi Furuike Tetsuya Tamura Hiroshi 《Research on Chemical Intermediates》2018,44(8):4971-4987
Research on Chemical Intermediates - A novel gel electrolyte has been prepared using bacterial cellulose (BC) coated with chitosan (CTS) and alginate (Alg) layers, which contain... 相似文献
169.
The Total Synthesis of Starfish Ganglioside GP3 Bearing a Unique Sialyl Glycan Architecture
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Kenta Goto Maki Sawa Dr. Hideki Tamai Dr. Akihiro Imamura Dr. Hiromune Ando Dr. Hideharu Ishida Dr. Makoto Kiso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8323-8331
The total synthesis of ganglioside GP3, which is found in the starfish Asterina pectinifera, has been accomplished through stereoselective and effective glycosylation reactions. The sialic acid embedded octasaccharide moiety of the target compound was constructed by [4+4] convergent coupling. A tetrasaccharyl donor and acceptor that contained internal sialic acid residues were synthesized with an orthogonally protected N‐Troc sialic acid donor as the key common synthetic unit, and they underwent highly stereoselective glycosidation. The resulting sialosides were subsequently transformed into reactive glycosyl acceptors. [4+4] coupling furnished the octasaccharide framework in 91 % yield as a single stereoisomer. Final conjugation of the octasaccharyl donor and glucosyl ceramide acceptor produced the protected target compound in high yield, which underwent global deprotection to successfully deliver ganglioside GP3. 相似文献
170.