全文获取类型
收费全文 | 1397篇 |
免费 | 30篇 |
国内免费 | 5篇 |
专业分类
化学 | 997篇 |
晶体学 | 11篇 |
力学 | 16篇 |
数学 | 54篇 |
物理学 | 354篇 |
出版年
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 15篇 |
2020年 | 11篇 |
2019年 | 22篇 |
2017年 | 11篇 |
2016年 | 16篇 |
2015年 | 12篇 |
2014年 | 25篇 |
2013年 | 85篇 |
2012年 | 40篇 |
2011年 | 53篇 |
2010年 | 27篇 |
2009年 | 40篇 |
2008年 | 68篇 |
2007年 | 65篇 |
2006年 | 57篇 |
2005年 | 49篇 |
2004年 | 50篇 |
2003年 | 70篇 |
2002年 | 51篇 |
2001年 | 32篇 |
2000年 | 47篇 |
1999年 | 31篇 |
1998年 | 22篇 |
1997年 | 21篇 |
1996年 | 17篇 |
1995年 | 10篇 |
1994年 | 22篇 |
1993年 | 15篇 |
1992年 | 41篇 |
1991年 | 20篇 |
1990年 | 19篇 |
1989年 | 21篇 |
1988年 | 25篇 |
1987年 | 26篇 |
1986年 | 18篇 |
1985年 | 28篇 |
1984年 | 22篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 19篇 |
1980年 | 15篇 |
1979年 | 28篇 |
1978年 | 22篇 |
1977年 | 13篇 |
1976年 | 12篇 |
1975年 | 12篇 |
1974年 | 13篇 |
1973年 | 20篇 |
排序方式: 共有1432条查询结果,搜索用时 437 毫秒
101.
ABSTRACT Coupling of the sodium salt of S-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-galacto-2-nonulopyranosylonate)-(2→'6)-2,3,4-tri-O-acetyl-1,6-dithio-β-D-glucopyranose (5), -β-D-galactopyranose (8), or S-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→'6)-O-(2,3,4-tri-O-acetyl-6-thio-β-D-galactopyranosyl)-(1→'4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranose (12), which were prepared from the corresponding 1-hydroxy compounds, 1, 2, and 9, via 1-chlorination, displacement with thioacetyl group, and S-deacetylation, with (2S,3R,4E)-2-azido-3-O-benzoyl-1-O-(p-toluenesulfonyl)-4-octadecene-1,3-diol (13), gave the corresponding β-thioglycosides 14, 18 and 22, respectively in good yields. The β-thioglycosides obtained were converted, via selective reduction of the azide group, condensation with octadecanoic acid, and removal of the protecting groups, into the title compounds. 相似文献
102.
Kuniaki Marui Yuuki Higashiura Shintaro Kodama Suguru Hashidate Akihiro Nomoto Shigenobu Yano Michio Ueshima Akiya Ogawa 《Tetrahedron》2014
The oxidation of alcohols using catalytic amounts of metal complexes is highly attractive from the viewpoint of green chemistry principles. However, examples of metal complex-catalyzed oxidations of alcohols with O2 using water as the solvent are still rare, and precious metals, high-pressure O2 or air, and a stoichiometric amount of base are often required. In this study, it was found that an oxovanadium-4,4′-t-Bubpy (4,4′-di-tert-butyl-2,2′-bipyridyl) complex exhibited high catalytic activity in the oxidation of benzhydrols under an atmosphere of O2 in water as the sole solvent. Interestingly, this catalytic oxidation method could be applied to the gram-scale aerobic oxidation of alcohols in water under the atmosphere. 相似文献
103.
Tomohiro Sakata Shingo Ogawa Keiko Inoue Yumiko Shimizu Yusaku Tanahashi 《Surface and interface analysis : SIA》2022,54(6):661-666
To systematically evaluate the quality of SiNx films in multi-stacked structures, we investigated the effects of post-deposition annealing (PDA) on the film properties of SiNx within the SiO2/SiNx/SiO2/Si stacked structure by performing X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), Fourier transform infrared (FT-IR) spectroscopy, and scanning transmission electron microscope–electron energy loss spectroscopy (STEM-EELS) analyses. The XPS results showed that PDA induces the oxidation of the SiNx layer. In particular, new finding is that Si-rich SiNx in the SiNx layer is preferentially oxidized by PDA even in multi-stacked structure. The XRR results showed that the SiNx layer becomes thinner, whereas the interface layer between the SiNx layer and Si becomes thicker. It is concluded by STEM-EELS and XPS that this interface layer is SiON layer. The density of N–H and Si–H bonding within the stacked structure strongly depends on the PDA temperature. Our study helps elucidate the properties of SiNx films in stacked structures from various perspectives. 相似文献
104.
Yu Ogawa Hitomi Hidaka Satoshi Kimura Ung-Jin Kim Shigenori Kuga Masahisa Wada 《Cellulose (London, England)》2014,21(2):999-1006
We investigated the crystal structure of alkali-celluloses, Na-cellulose IIA and II(Cu), formerly known as Na-cellulose IIB, by synchrotron X-ray diffraction. Na-cellulose IIA, formed from cellulose I by high-concentration NaOH treatment, has a fiber repeat of 15 Å and a threefold-like helical conformation. Na-cellulose II(Cu), prepared by treating cellulose I with copper-saturated alkali solution, also has a fiber repeat of 15 Å with threefold helical symmetry. Incorporation of Cu(II) ions into cellulose was confirmed by multiwavelength anomalous diffraction. Monitoring by X-ray diffraction revealed that the formation of this complex from cellulose I is remarkably slow, probably because of the involvement of copper ion. The stability of alkali-cellulose II(Cu) was tested to estimate the influence of the presence of copper in the crystal. Na-cellulose II(Cu) characteristically dissolved in aqueous ammonia solution, indicating strong coordination of copper ion to cellulose. 相似文献
105.
Non‐Heme Dioxygenase Catalyzes Atypical Oxidations of 6,7‐Bicyclic Systems To Form the 6,6‐Quinolone Core of Viridicatin‐Type Fungal Alkaloids
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)
Noriyasu Ishikawa Dr. Hidenori Tanaka Dr. Fumi Koyama Prof. Dr. Hiroshi Noguchi Prof. Dr. Clay C. C. Wang Prof. Dr. Kinya Hotta Prof. Dr. Kenji Watanabe 《Angewandte Chemie (International ed. in English)》2014,53(47):12880-12884
The 6,6‐quinolone scaffold of the viridicatin‐type of fungal alkaloids are found in various quinolone alkaloids which often exhibit useful biological activities. Thus, it is of interest to identify viridicatin‐forming enzymes and understand how such alkaloids are biosynthesized. Here an Aspergillal gene cluster responsible for the biosynthesis of 4′‐methoxyviridicatin was identified. Detailed in vitro studies led to the discovery of the dioxygenase AsqJ which performs two distinct oxidations: first desaturation to form a double bond and then monooxygenation of the double bond to install an epoxide. Interestingly, the epoxidation promotes non‐enzymatic rearrangement of the 6,7‐bicyclic core of 4′‐methoxycyclopenin into the 6,6‐quinolone viridicatin scaffold to yield 4′‐methoxyviridicatin. The finding provides new insight into the biosynthesis of the viridicatin scaffold and suggests dioxygenase as a potential tool for 6,6‐quinolone synthesis by epoxidation of benzodiazepinediones. 相似文献
106.
Daisuke Saito Dr. Tomohiro Ogawa Dr. Masaki Yoshida Junichi Takayama Dr. Satoshi Hiura Prof. Dr. Akihiro Murayama Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18882-18889
A series of assembled PtII complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups, [Pt(CN)2(R-impy)] (R-impyH+=1-alkyl-3-(2-pyridyl)-1H-imidazolium, R=Me ( Pt-Me ), Et ( Pt-Et ), iPr ( Pt- i Pr ), and tBu ( Pt- t Bu )). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield of 0.51–0.81 in the solid state at room temperature, originating from the triplet metal-metal-to-ligand charge transfer (3MMLCT) state. Their emission colors cover the entire visible region from red for Pt-Me to blue for Pt- t Bu . Importantly, Pt- t Bu is the first example that exhibits blue 3MMLCT emission. The 3MMLCT emission was proved and characterized based on the temperature dependences of the crystal structures and emission properties. The wide-range color tuning of luminescence using the 3MMLCT emission presents a new strategy of superfine control of the emission color. 相似文献
107.
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
108.
Simultaneous Delamination and Rutile Formation on the Surface of Ti3C2Tx MXene for Copper Adsorption
In this work, we studied the formation of the rutile phase of titanium dioxide (TiO2) on delaminated MXene (d‐Ti3C2Tx) flakes by the reaction of Ti3C2Tx with amino acids in water. Three types of amino acids with varied side‐chain polarity were used to delaminate Ti3C2Tx. d‐Ti3C2Tx flakes formed stable colloidal solutions due to the negative surface charges of chemisorbed amino acids on the d‐Ti3C2Tx. Rutile formed on d‐Ti3C2Tx at room temperature upon the intercalation of aromatic amino acids and subsequent sonication of the solution, while flakes intercalated with aliphatic amino acids did not oxidize. X‐Ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy revealed the nanosize rutile formation on the surface of Ti3C2Tx flakes. The XPS results indicated the surface functionalization of histidine on d‐Ti3C2Tx flakes. As‐synthesized histidine functionalized rutile TiO2@d‐Ti3C2Tx hybrid was used for adsorption of Cu2+ ions from aqueous solution with a maximum uptake of 95 mg g?1. 相似文献
109.
110.
Masahito Sekiguchi Hiromichi Tanaka Noriaki Takami Akiya Ogawa Ilhyong Ryu Noboru Sonoda 《Heteroatom Chemistry》1991,2(3):427-430
The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se2− and Se22−), the alkylation of which provided dialkyl selenides and diselenides, respectively, in excellent yields. 相似文献