全文获取类型
收费全文 | 1033篇 |
免费 | 39篇 |
国内免费 | 3篇 |
专业分类
化学 | 776篇 |
晶体学 | 5篇 |
力学 | 6篇 |
数学 | 79篇 |
物理学 | 209篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 6篇 |
2016年 | 22篇 |
2015年 | 16篇 |
2014年 | 18篇 |
2013年 | 32篇 |
2012年 | 43篇 |
2011年 | 64篇 |
2010年 | 34篇 |
2009年 | 33篇 |
2008年 | 69篇 |
2007年 | 72篇 |
2006年 | 43篇 |
2005年 | 49篇 |
2004年 | 58篇 |
2003年 | 63篇 |
2002年 | 39篇 |
2001年 | 20篇 |
2000年 | 22篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 15篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1992年 | 15篇 |
1991年 | 14篇 |
1990年 | 17篇 |
1989年 | 12篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 14篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 10篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 6篇 |
1976年 | 15篇 |
1975年 | 17篇 |
1974年 | 5篇 |
1972年 | 4篇 |
排序方式: 共有1075条查询结果,搜索用时 24 毫秒
21.
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
22.
Ito S Nomura A Morita N Kabuto C Kobayashi H Maejima S Fujimori K Yasunami M 《The Journal of organic chemistry》2002,67(21):7295-7302
The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement. 相似文献
23.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
24.
The titled [3]radialenes are the first, water-soluble hexaaryl[3]radialenes with considerably high electron affinity, their alkali metal reduction giving rise to anion-radicals and dianions stepwise as fairly stable species in degassed tetrahydrofuran. 相似文献
25.
Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed. 相似文献
26.
Matsuura K Ikoma S Sugiyama M Funauchi M Sinohara H 《Applied biochemistry and biotechnology》2000,83(1-3):107-114
Polyclonal Immunoglobulin (Ig) G from patients with rheumatoid arthritis (RA) and healthy subjects hydrolyzed carbobenzoxy−Val−Gly−Arg
p-nitroanilide and D−Pro−Phe−Arg p-nitroanilide. RA IgG exhibited higher activity against the former substrate, but not the latter. On the other hand, RA IgG
showed reduced activity against D−Pro−Phe−Arg methylcoumarinamide, when compared with those of the healthy controls. These
results suggest that RA IgGs differ from normal IgGs in the substrate specificity of amidase activity. Preliminary studies
have shown that two out of three RA IgG samples cleaved a pentapeptide—Gln−Arg−Arg−Arg−Ala−Ala— which is assumed to be associated
with the risk of developing RA (Gregersen, P. K. et al. (1987), Arthritis Rheum.
30, 1205–1213). By contrast, virtually no cleavage of the same peptide was observed with IgG from healthy controls. A peptide
analog, Gln−Arg−Arg−Trp−Ala, was not cleaved at all by any IgGs examined either from RA patients or healthy controls. 相似文献
27.
(-)-Pestalotin [(6S, l'S)-6-(1'-hydroxypentyl)-4-methoxy-5,6-d dihydro-2-pyrone 1a]and its three other stereoisomers were synthesized either by utilizing the Sharpless asymmetric epoxidation as the keystep or by derivation from D-(+)-glyceraldehyde acetonide. 相似文献
28.
Katayama H Ishihama Y Oda Y Asakawa N 《Rapid communications in mass spectrometry : RCM》2000,14(14):1167-1178
A novel method for electrophoretic mobility-assisted identifications of proteins, using capillary electrophoresis/mass spectrometry (CE/MS) under methanolic conditions, was developed. The number of functional groups of the enzymatic digest peptides was estimated from a single run CE/MS analysis and utilized as an additional tag for database searching in addition to the mass map of the peptides. The additional amino acid information thus obtained can improve the confidence level of the protein identification. The database searching software algorithm ProFound was modified to accept the tag, based on this new concept. In this study, optimization of the CE/MS conditions for the estimation of basic functional groups was performed as an example. An accurate value of the number of such functional groups was obtained from CE characteristics when methanolic buffer (methanol/formic acid/water = 60:20:20) was used, via an excellent correlation (r = 0.997) between the number of functional groups of the peptides and [MW((2/3))]. The mass spectrometry sensitivity was also improved when using the methanolic buffer in comparison with that obtained using aqueous 1% formic acid buffer. The identification of a protein of Saccharomyces cerevisiae, which was separated by two-dimensional electrophoresis, was performed using the methanolic buffer in combination with sheathless nanoelectrospray CE/MS. A protein spot that had not been identified by MALDI-TOFMS and LC/MS/MS was successfully identified using this new method. 相似文献
29.
Photoinduced morphism of gemini surfactant aggregates 总被引:5,自引:0,他引:5
Faure D Gravier J Labrot T Desbat B Oda R Bassani DM 《Chemical communications (Cambridge, England)》2005,(9):1167-1169
The photochemical behaviour of an azobenzene chromophore inserted in a gemini surfactant imparts photocontrol to the resulting amphiphile assemblies, including the collapse, upon irradiation, of the multi lamellar vesicles formed in aqueous solution. 相似文献
30.
Miyabe H Nishimura A Ueda M Naito T 《Chemical communications (Cambridge, England)》2002,(14):1454-1455
The indium-mediated allylation and alkylation reactions of the Oppolzer camphorsultam derivative of glyoxylic oxime ether proceeded with excellent diastereoselectivity in aqueous media, providing a variety of enantiomerically pure alpha-amino acids. 相似文献