全文获取类型
收费全文 | 1248篇 |
免费 | 103篇 |
国内免费 | 4篇 |
专业分类
化学 | 1082篇 |
晶体学 | 15篇 |
力学 | 27篇 |
数学 | 53篇 |
物理学 | 178篇 |
出版年
2023年 | 16篇 |
2022年 | 21篇 |
2021年 | 27篇 |
2020年 | 31篇 |
2019年 | 26篇 |
2018年 | 35篇 |
2017年 | 20篇 |
2016年 | 54篇 |
2015年 | 44篇 |
2014年 | 68篇 |
2013年 | 74篇 |
2012年 | 110篇 |
2011年 | 150篇 |
2010年 | 71篇 |
2009年 | 66篇 |
2008年 | 96篇 |
2007年 | 72篇 |
2006年 | 73篇 |
2005年 | 55篇 |
2004年 | 55篇 |
2003年 | 46篇 |
2002年 | 32篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1978年 | 3篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1931年 | 1篇 |
排序方式: 共有1355条查询结果,搜索用时 281 毫秒
131.
A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State
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)
Dr. Daisuke Sakamaki Soichiro Yano Toshiyuki Kobashi Prof. Dr. Shu Seki Dr. Takuya Kurahashi Prof. Dr. Seijiro Matsubara Dr. Akihiro Ito Prof. Dr. Kazuyoshi Tanaka 《Angewandte Chemie (International ed. in English)》2015,54(28):8267-8270
Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor. 相似文献
132.
A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes
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)
Dr. Yoichi Hoshimoto Takuya Kinoshita Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2015,54(40):11666-11671
N‐Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. 相似文献
133.
Total Synthesis and Biological Evaluation of the Antibiotic Lysocin E and Its Enantiomeric,Epimeric, and N‐Demethylated Analogues
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)
Dr. Motoki Murai Takuya Kaji Dr. Takefumi Kuranaga Dr. Hiroshi Hamamoto Prof. Dr. Kazuhisa Sekimizu Prof. Dr. Masayuki Inoue 《Angewandte Chemie (International ed. in English)》2015,54(5):1556-1560
Lysocin E, a macrocyclic peptide, exhibits potent antibacterial activity against methicillin‐resistant Staphylococcus aureus (MRSA) through a novel mechanism. The first total synthesis of lysocin E was achieved by applying a full solid‐phase strategy. The developed approach also provides rapid access to the enantiomeric, epimeric, and N‐demethylated analogues of lysocin E. Significantly, the antibacterial activity of the unnatural enantiomer was comparable to that of the natural isomer, suggesting the absence of chiral recognition in its mode of action. 相似文献
134.
Zhe Sun Parantap Sarkar Takuya Suenaga Sota Sato Hiroyuki Isobe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(43):12991-12995
The recent development of cyclo‐para‐phenylenes has demonstrated the feasibility of radial π systems in nanohoop structures, especially in the crystalline state. However, in contrast to macrocyclic molecules with benzene units, which have a several‐decades‐long history, macrocycles composed solely of naphthylene units (the smallest acene) have been much less explored. Although two examples of cyclonaphthylenes have been reported to date, neither possesses a radial π system. We herein report the first example of belt‐shaped cyclonaphthylenes with curved π systems. The molecule, [8]cyclo‐amphi‐naphthylene, is linked at the 2,6‐positions of the naphthylene units, thus affording belt‐shaped molecules. Although the molecular structures are flexible, which allows for rotation of the naphthylene units in solution, they can be rigidified with the aid of methylene bridges to afford persistent molecular structures in solution. 相似文献
135.
The normal impact of single water drops onto a plane water surface was studied experimentally to reveal the amount of secondary drops produced from the rim of crown-like interfacial structure. Within the experimental ranges tested, the ratio of the total mass of secondary drops to the mass of primary drop was approximately within 0–1 and correlated well as the function of dimensionless parameter K that consisted of the impact Weber number We and the Ohnesorge number Oh (K = We Oh
−0.4). The dependences of the number and the mean diameter of secondary drops on K and dimensionless film thickness were also investigated. 相似文献
136.
Miki ItoFujiko Konno Takuya KumamotoNoriyuki Suzuki Masatoshi KawahataKentaro Yamaguchi Tsutomu Ishikawa 《Tetrahedron》2011,67(41):8041-8049
Both enantiomers of chelidonine, a B/C-cis-11-hydroxyhexahydrobenzo[c]phenanthridine alkaloid, were synthesized by manipulation of the B/C-dehydro ring juncture of benzo[c]phenanthridine skeleton using Sharpless asymmetric dihydroxylation and stereospecific catalytic hydrogenation after introduction of oxygen functions on the C ring as key reaction steps for the construction of stereogenic centers. 相似文献
137.
Takuya OkadaKazuhiko Sakaguchi Tetsuro ShinadaYasufumi Ohfune 《Tetrahedron letters》2011,52(44):5744-5746
The stereoselective total synthesis of (−)-funebrine from 2-butyn-1-ol was described. The crucial steps in the synthesis involved the stereoselective enolate Claisen rearrangement of the (S)-α-acyloxy-α-alkynylsilane 8, the Au-catalyzed regio- and stereoselective lactonization of the allenylsilane 7, and the Paal-Knorr pyrrole condensation using an unsymmetrical 1,4-diketone 4b. 相似文献
138.
139.
Highly photoluminescent nanocrystals based on a gold(I) complex and their electrophoretic patterning
Saitoh M Balch AL Yuasa J Tada K Onoda M Nakashima T Kawai T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10947-10952
The fabrication of nanocrystals (NCs) composed of the cationic Au(I) complex was demonstrated by the reprecipitation method in which the colloidal solution of the NCs showed brilliant green phosphorescence with a quantum yield of 83% in n-hexane. Characterization of the prepared NCs was performed by transmission electron microscopy observation and elemental analysis with energy-dispersive X-ray spectroscopy. The obtained Au(I) NCs were particles of random shapes with a diameter of 200-400 nm. The selected-area electron diffraction and X-ray diffraction measurements showed the characteristic diffraction patterns attributable to the crystal structure of the bulk crystal of the Au(I) complex. A similar method was performed with a different counteranion, leading to a colloidal solution of the microcrystals (MCs) with brilliant yellow phosphorescence and a quantum yield of 26% in n-hexane. Luminescence patterning of the NCs and MCs was also achieved successfully by electrophoretic deposition onto an indium tin oxide (ITO)-coated glass substrate, resulting in characteristic luminescence patterns on the ITO substrates with relatively high photoluminescence quantum yields. 相似文献
140.
Kitano H Kondo T Kamada T Iwanaga S Nakamura M Ohno K 《Colloids and surfaces. B, Biointerfaces》2011,88(1):455-462
An amphoteric copolymer brush of methacrylic acid (MA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) was prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization using both a free chain transfer agent (n-butylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid) and a radical initiator (4,4'-azobis(4-cyanopentanoic acid)) covalently fixed to a glass substrate. An aqueous solution of the copolymer, Poly(MA-r-DMAEMA), which was simultaneously obtained in liquid phase, had a sufficiently small polydispersity in its molecular weight. The copolymer brush showed effective suppression of non-specific adsorption of bovine serum albumin and egg white lysozyme to the brush. In contrast, both negatively charged PolyMA and positively charged PolyDMAEMA brushes significantly adsorbed the proteins irrespective of their net charges. Upon ion beam irradiation, furthermore, a hollow space with a designed shape could be made on the glass substrate, and both HEK293 and HepG2 cells non-specifically adhered to the space, forming aggregates, while no adhesion to the non-treated area on the brush was observed. These results suggest that the amphoteric polymer brushes will be useful materials for biomedical applications. 相似文献