全文获取类型
收费全文 | 1265篇 |
免费 | 99篇 |
国内免费 | 5篇 |
专业分类
化学 | 1082篇 |
晶体学 | 14篇 |
力学 | 15篇 |
数学 | 73篇 |
物理学 | 185篇 |
出版年
2023年 | 16篇 |
2022年 | 13篇 |
2021年 | 29篇 |
2020年 | 31篇 |
2019年 | 25篇 |
2018年 | 34篇 |
2017年 | 19篇 |
2016年 | 53篇 |
2015年 | 44篇 |
2014年 | 68篇 |
2013年 | 69篇 |
2012年 | 110篇 |
2011年 | 159篇 |
2010年 | 70篇 |
2009年 | 67篇 |
2008年 | 96篇 |
2007年 | 76篇 |
2006年 | 69篇 |
2005年 | 55篇 |
2004年 | 56篇 |
2003年 | 50篇 |
2002年 | 32篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 11篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 9篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1965年 | 1篇 |
1964年 | 2篇 |
排序方式: 共有1369条查询结果,搜索用时 187 毫秒
131.
Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework 下载免费PDF全文
Dr. Takuya Higo Tomoya Ukegawa Dr. Satoshi Yokoshima Prof. Tohru Fukuyama 《Angewandte Chemie (International ed. in English)》2015,54(25):7367-7370
An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis. 相似文献
132.
Hydrogen Production from a Methanol–Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions 下载免费PDF全文
Prof. Dr. Ken‐ichi Fujita Dr. Ryoko Kawahara Takuya Aikawa Prof. Dr. Ryohei Yamaguchi 《Angewandte Chemie (International ed. in English)》2015,54(31):9057-9060
An efficient catalytic system for the production of hydrogen from a methanol–water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L?1 NaOH) below 100 °C] without the use of an additional organic solvent. Long‐term continuous hydrogen production from a methanol–water solution catalyzed by the anionic iridium complex was also achieved. 相似文献
133.
A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State 下载免费PDF全文
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
134.
A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes 下载免费PDF全文
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
135.
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
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
136.
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
137.
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
138.
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
139.
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
140.