全文获取类型
收费全文 | 438篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 330篇 |
晶体学 | 7篇 |
力学 | 3篇 |
数学 | 19篇 |
物理学 | 100篇 |
出版年
2023年 | 6篇 |
2022年 | 1篇 |
2021年 | 6篇 |
2020年 | 15篇 |
2019年 | 11篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 10篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 15篇 |
2012年 | 28篇 |
2011年 | 26篇 |
2010年 | 12篇 |
2009年 | 16篇 |
2008年 | 30篇 |
2007年 | 24篇 |
2006年 | 27篇 |
2005年 | 33篇 |
2004年 | 29篇 |
2003年 | 25篇 |
2002年 | 19篇 |
2001年 | 8篇 |
2000年 | 7篇 |
1999年 | 15篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1985年 | 3篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1976年 | 4篇 |
1973年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有459条查询结果,搜索用时 453 毫秒
81.
82.
Akimichi Ohtsuki Masafumi Minoshima Maki Ikeda Hiroki Nagase Hiroshi Sugiyama 《Tetrahedron letters》2009,50(52):7288-2828
We have designed and synthesized new types of pyrrole (P)-imidazole (I) polyamide conjugates 1 and 2 possessing a suberoylanilide hydroxamic acid (SAHA) moiety that is a strong inhibitor of histone deacetylase (HDAC). SAHA conjugate 2 was designed to target the promoter region of the p16 tumor suppressor gene. The DNA binding affinity of SAHA conjugate 2 to its target sequence was examined using surface plasmon resonance. HDAC inhibition activity of conjugates 1 and 2 was evaluated using a colorimetric assay. The results demonstrated that even though it possesses the relatively large SAHA moiety, conjugate 2 has high DNA sequence-specific binding properties and moderate HDAC inhibitory activity in vitro. SAHA conjugate 2 was found to cause morphological changes in HeLa cells and to induce selective Histone H3 lysine 9 acetylation. 相似文献
83.
The question as to whether state-selective population of molecular vibrational levels by shaped infrared laser pulses is possible in a condensed phase environment is of central importance for such diverse fields as time-resolved spectroscopy, quantum computing, or "vibrationally mediated chemistry." This question is addressed here for a model system, representing carbon monoxide adsorbed on a Cu(100) surface. Three of the six vibrational modes are considered explicitly, namely, the CO stretch vibration, the CO-surface vibration, and a frustrated translation. Optimized infrared pulses for state-selective excitation of "bright" and "dark" vibrational levels are designed by optimal control theory in the framework of a Markovian open-system density matrix approach, with energy flow to substrate electrons and phonons, phase relaxation, and finite temperature accounted for. The pulses are analyzed by their Husimi "quasiprobability" distribution in time-energy space. 相似文献
84.
Hirohara S Obata M Ogata S Kajiwara K Ohtsuki C Tanihara M Yano S 《Journal of photochemistry and photobiology. B, Biology》2006,84(1):56-63
In order to explore the influence of the sugar moieties of glycoconjugated chlorins on the photocytotoxicity, we studied the photochemical properties of four glycoconjugated chlorins in aqueous media such as cytoplasm and the concentration dependence of photocytotoxicity in HeLa cells. In phosphate-buffered saline, the fluorescence intensities of 5,10,15,20-tetrakis[3-(beta-D-glucopyranosyloxy)phenyl]chlorin (m-1a) and 5,10,15,20-tetrakis[3-(beta-D-galactopyranosyloxy)phenyl]chlorin (m-1b), i.e., chlorins having hexose groups, were about 2-fold greater than those of 5,10,15,20-tetrakis[3-(beta-d-xylopyranosyloxy)phenyl]chlorin (m-1c) and 5,10,15,20-tetrakis[3-(beta-d-arabinopyranosyloxy)phenyl]chlorin (m-1d), i.e., chlorins having pentose groups, owing to a sugar-dependent difference of aggregation behavior. While no cytotoxicity was found in the dark, the highest photocytotoxicity was shown by m-1a (82% inhibition) in HeLa cells. This was higher than those of m-1b, m-1c, m-1d and tetraphenylporphyrin tetrasulfonic acid. The glycoconjugated chlorins except for m-1b appeared to be distributed diffusely throughout the cytoplasm. Among the four photosensitizers, m-1a showed the highest intensity in confocal fluorescence images, in agreement with the in vitro photocytotoxicity results. For m-1c, no photocytotoxicity was found at drug concentrations from 0.2 to 0.04 microM. Hence, sugar-dependent aggregation is not the major reason for the unexpected lack of efficacy of m-1c, which is uptaken efficiently by HeLa cells. For the glycoconjugated chlorins, these results suggest the biological aspects of sugar moiety play much crucial role rather than chemical aspects. 相似文献
85.
The spin mixing process of the radical pair in the sodium dodecyl sulfate (SDS) micelle is studied by using a novel technique nanosecond pulsed magnetic field effect on transient absorption. We have developed the equipment for a nanosecond pulsed magnetic field and observed its effect on the radical pair reaction. A decrease of the free radical yield by a reversely directed pulsed magnetic field that cancels static field is observed, and the dependence on its magnitude, which is called pulsed MARY (magnetic field effect on reaction yield) spectra, is studied. The observed spectra reflect the spin mixing in 50-200 ns and show clear time evolution. Theoretical simulation of pulsed MARY spectra based on a single site modified Liouville equation indicates that the fast spin dephasing processes induced by the modulation of electron-electron spin interaction by molecular reencounter affect to the coherent spin mixing by a hyperfine interaction in a low magnetic field. 相似文献
86.
Direct numerical simulation of elastic turbulence and its mixing-enhancement effect in a straight channel flow 下载免费PDF全文
In this paper,we present a direct numerical simulation(DNS) of elastic turbulence of viscoelastic fluid at vanishingly low Reynolds number(Re = 1) in a three-dimensional straight channel flow for the first time,using the Giesekus constitutive model for the fluid.In order to generate and maintain the turbulent fluid motion in the straight channel,a sinusoidal force term is added to the momentum equation,and then the elastic turbulence is numerically realized with an initialized chaotic velocity field and a stretched conformation field.Statistical and structural characteristics of the elastic turbulence therein are analyzed based on the detailed information obtained from the DNS.The fluid mixing enhancement effect of elastic turbulence is also demonstrated for the potential applications of this phenomenon. 相似文献
87.
A novel method for the preparation of N-acylpyrrole is described. The method involves condensation of carboxylic acids with 2,4,4-trimethoxybutan-1-amine, followed by acid-mediated cyclization to form the pyrrole ring. The preparative procedure is highly tolerant of a variety of functional groups. 相似文献
88.
A cationic CpRu complex of chiral picolinic acid derivatives [(R)- or (S)-Cl-Naph-PyCOOCH(2)CH═CH(2)] catalyzes asymmetric intramolecular dehydrative N-allylation of N-substituted ω-amino- and -aminocarbonyl allylic alcohols with a substrate/catalyst ratio of up to 2000 to give α-alkenyl pyrrolidine-, piperidine-, and azepane-type N-heterocycles with an enantiomer ratio of up to >99:1. The wide range of applicable N-substitutions, including Boc, Cbz, Ac, Bz, acryloyl, crotonoyl, formyl, and Ts, significantly facilitates further manipulation toward natural product synthesis. 相似文献
89.
90.
Yokoi T Kato H Kim IY Kikuta K Kamitakahara M Kawashita M Ohtsuki C 《Dalton transactions (Cambridge, England : 2003)》2012,41(9):2732-2737
Octacalcium phosphates (OCPs) co-incorporated with various molar ratios of succinate and suberate ions were synthesized by wet processing. The interplanar spacings of the (100) planes (d(100)) of OCPs formed in the presence of succinic acid (Suc) or suberic acid (Sub) were larger than those of OCPs formed without addition of a dicarboxylic acid to the reaction solvent. The increases in the interplanar spacings of the (100) planes were caused by substitution of HPO(4)(2-) by dicarboxylate ions. The OCPs with co-incorporated succinate and suberate ions, i.e. solid solutions of OCP with incorporated Suc and Sub, were formed by reactions in the presence of Suc and Sub. When the Suc/(Suc + Sub) values in the starting compositions were in the range 0.45-1.0, Suc was preferentially incorporated into the OCP. In contrast, when the Sub/(Suc + Sub) values in the starting compositions were in the range 0.60-1.0, Sub was preferentially incorporated into the OCP crystals. 相似文献