全文获取类型
收费全文 | 760篇 |
免费 | 30篇 |
国内免费 | 2篇 |
专业分类
化学 | 500篇 |
晶体学 | 4篇 |
力学 | 5篇 |
数学 | 39篇 |
物理学 | 244篇 |
出版年
2023年 | 7篇 |
2022年 | 5篇 |
2021年 | 9篇 |
2020年 | 15篇 |
2019年 | 18篇 |
2018年 | 7篇 |
2017年 | 7篇 |
2016年 | 21篇 |
2015年 | 16篇 |
2014年 | 17篇 |
2013年 | 43篇 |
2012年 | 41篇 |
2011年 | 48篇 |
2010年 | 24篇 |
2009年 | 22篇 |
2008年 | 30篇 |
2007年 | 24篇 |
2006年 | 43篇 |
2005年 | 58篇 |
2004年 | 45篇 |
2003年 | 34篇 |
2002年 | 39篇 |
2001年 | 28篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 9篇 |
1995年 | 9篇 |
1994年 | 12篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 10篇 |
1986年 | 8篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 4篇 |
1965年 | 2篇 |
1938年 | 1篇 |
排序方式: 共有792条查询结果,搜索用时 0 毫秒
11.
Konda-Yamada Y Asano K Satou T Monma S Sakayanagi M Satou N Takeda K Harigaya Y 《Chemical & pharmaceutical bulletin》2005,53(5):529-536
Oxopropyl E-(pyrrolidine-2-ylidene)glycinamide (5c) and allyl E-(pyrrolidine-2-ylidene)glycinate (5d) were effectively synthesized from 2,3,5-tri-O-benzyl-4-O-tert-butyldimethylsilyl(TBDMS)-D-arabinal (7) using intramolecular 1,3-dipolar cyclic reaction of azide and olefin as a key reaction. These results proved this cyclic reaction should be applicable for the synthesis of various (pyrrolidine-2-ylidene)glycinate and glycinamide. In addition, the development of a synthetic route for the precursor of an unsaturated cyclic dehydro amino acid involved in azinomycins (carzinophilin) using relating glycinate, methyl E-(pyrrolidine-2-ylidene)glycinate (5a) was described. 相似文献
12.
The development of near-infrared (NIR) fluorescent probes over the past few decades has changed the way that biomolecules are imaged, and thus represents one of the most rapidly progressing areas of research. Presently, NIR fluorescent probes are routinely used to visualize and understand intracellular activities. The ability to penetrate tissues deeply, reduced photodamage to living organisms, and a high signal-to-noise ratio characterize NIR fluorescent probes as efficient next-generation tools for elucidating various biological events. The coupling of self-labeling protein tags with synthetic fluorescent probes is one of the most promising research areas in chemical biology. Indeed, at present, protein-labeling techniques are not only used to monitor the dynamics and localization of proteins but also play a more diverse role in imaging applications. For instance, one of the dominant technologies employed in the visualization of protein activity and regulation is based on protein tags and their associated NIR fluorescent probes. In this mini-review, we will discuss the development of several NIR fluorescent probes used for various protein-tag systems.This minireview describes the development of NIR chemical probes for various protein-tag systems. 相似文献
13.
Nagao M Asano K Umeda K Katayama H Ozawa F 《The Journal of organic chemistry》2005,70(25):10511-10514
[reaction: see text] Complex 1 bearing a diphosphinidenecyclobutene ligand (DPCB-OMe) catalyzes highly stereoselective hydrosilylation of diethynylarenes with HSiMe2Ph to afford (Z,Z)-bis(2-silylethenyl)arenes. Treatment of the hydrosilylation products with N-bromosuccinimide causes bromodesilylation in a stereospecific manner, giving (Z,Z)-bis(2-bromoethenyl)arenes in high geometrical purity (>98%). 相似文献
14.
The conjugate addition reactions of BHA alkenoates with organolithiums in toluene or toluene-hexane at −78 °C were mediated by the chiral ligands 1 and 2 to give the corresponding 3-substituted alkanoates in high ees and high yields. The two ligands are complementary each other, 1 is effective for phenyl- and vinyllithiums to give the adducts in 64–93% ee, while 2 is effective for butyl- and ethyllithiums to give the adducts in 91–99% ee. 相似文献
15.
Nitration of aromatic halides proceeded smoothly in the presence of catalytic amounts of Cu bronze and N,N′-dimethylethylenediamine. Sodium nitrite-18-crown-6, or tetra-n-butylammonium nitrite (n-Bu4NNO2) turned out to be efficient nitrating agents. The aromatic nitro compounds were synthesized under essentially neutral conditions. 相似文献
16.
Jingye Li Kohei Sato Saneto Asano Minoru Iida Yoneho Tabata Masakazu Washio 《European Polymer Journal》2005,41(3):547-555
Crosslinked and non-crosslinked polytetrafluoroethylene films (RX-PTFE and V-PTFE films, respectively) were irradiated by γ-ray and then grafted with styrene in liquid phase. Microscope FT-IR spectroscopy, TGA, solid state 13C CP/MAS and high resolution HS/MAS NMR spectroscopy, wide-angle X-ray diffraction (WAXD) study were used to get the structural information of the styrene grafted RX-PTFE and V-PTFE films. From microscope FT-IR spectra of the grafted RX-PTFE films, the “grafting front mechanism” was proved. TGA analysis showed that the grafted films have a small degradation step and two main degradation steps. In the 13C CP/MAS NMR spectra of the non-grafted films, there are no signal due to the absence of the hydrogen atom. While in the spectra of the grafted films, there are signals attributed to the polystyrene grafts. In the 13C HS/MAS NMR spectra of the grafted films, the relative intensity of the peaks attributed to the polystyrene grafts increased while the relative intensity of the peak attributed to PTFE matrix decreased with the increase in the DOG. From WAXD patterns, the intensity of the crystalline peak decrease with the increase in the DOG. The grafted films were sulfonated by chlorosulfonic acid and the results of highest IEC value exceeded 3.0. Those results will be reported in the near future. 相似文献
17.
Yuichiro Hori Miyako Nishiura Tomomi Tao Reisuke Baba Steven D. Bull Kazuya Kikuchi 《Chemical science》2021,12(7):2498
Reversible enzymatic post-translational modification of the ε-amino groups of lysine residues (e.g. N-acylation reactions) plays an important role in regulating the cellular activities of numerous proteins. This study describes how enzyme catalyzed N-deprotection of lysine residues of non-fluorescent peptide-coumarin probes can be used to generate N-deprotected peptides that undergo spontaneous O- to N-ester transfer reactions (uncatalyzed) to generate a highly fluorescent N-carbamoyl peptide. This enables detection of enzyme catalyzed N-deacetylation, N-demalonylation, N-desuccinylation and N-demethylation reactions activities towards the N-modified lysine residues of these probes using simple ‘turn on’ fluorescent assays.We developed “turn-on” fluorescent probes that detect enzymatic lysine deacylation and demethylation critical for epigenetic and other cellular phenomena, using intramolecular O- to N-ester transfer reactions. 相似文献
18.
[structure:see text] The marine natural product hennoxazole A was synthesized by a convergent approach. The diastereoselective Mukaiyama aldol reaction with beta-alkoxy aldehyde was used to construct the tetrahydropyran segment, and the preparation of the nonconjugated triene moiety was accomplished via S(N)2 displacement of allylic bromide with vinyllithium and Takai's iodoolefination followed by palladium-catalyzed cross coupling with MeMgBr. The final steps involve an amide coupling using DEPC and oxazole synthesis via a oxidation/cyclodehydration process. 相似文献
19.
20.
Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available. 相似文献