全文获取类型
收费全文 | 152篇 |
免费 | 7篇 |
专业分类
化学 | 136篇 |
数学 | 3篇 |
物理学 | 20篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 3篇 |
2015年 | 7篇 |
2014年 | 2篇 |
2013年 | 9篇 |
2012年 | 13篇 |
2011年 | 7篇 |
2010年 | 9篇 |
2009年 | 5篇 |
2008年 | 16篇 |
2007年 | 11篇 |
2006年 | 11篇 |
2005年 | 7篇 |
2004年 | 7篇 |
2003年 | 7篇 |
2002年 | 3篇 |
2000年 | 1篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有159条查询结果,搜索用时 15 毫秒
71.
Inamura S Fujimoto Y Kawasaki A Shiokawa Z Woelk E Heine H Lindner B Inohara N Kusumoto S Fukase K 《Organic & biomolecular chemistry》2006,4(2):232-242
The peptidoglycan (PG) bacterial cell wall glycoconjugate has been well known as a strong immunopotentiator. Partial structures of PG were chemically synthesized for elucidation of precise biological activities. Effective construction of distinct repeating glycans of PG was accomplished by the coupling of a key disaccharide glucosaminyl-beta(1-4)-muramic acid unit. Stereoselective glycosylation of disaccharide units was achieved by neighboring group participation of the N-Troc (Troc = 2,2,2-trichloroethoxycarbonyl) group and appropriate reactivity of N-Troc-glucosaminyl trichloroacetimidate. By using an efficient synthetic strategy, mono-, di-, tetra- and octasaccharide fragments of PG were synthesized in high yields. The biological activity of synthetic fragments of PG was evaluated by induction of tumor necrosis factor-alpha (TNF-alpha) from human monocytes, and toll-like receptor 2 (TLR2) and Nod2 dependencies by using transfected HEK293 cells, respectively. Here we reveal that TLR2 was not stimulated by the series of synthetic PG partial structures, whereas Nod2 recognizes the partial structures containing the MDP moiety. 相似文献
72.
Tanaka M Sawaguchi T Sato Y Yoshioka K Niwa O 《Langmuir : the ACS journal of surfaces and colloids》2011,27(1):170-178
Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation. 相似文献
73.
Takahashi Y Obara R Lin ZZ Takahashi Y Naito T Inabe T Ishibashi S Terakura K 《Dalton transactions (Cambridge, England : 2003)》2011,40(20):5563-5568
The structural and electrical properties of a metal-halide cubic perovskite, CH(3)NH(3)SnI(3), have been examined. The band structure, obtained using first-principles calculation, reveals a well-defined band gap at the Fermi level. However, the temperature dependence of the single-crystal electrical conductivity shows metallic behavior down to low temperatures. The temperature dependence of the thermoelectric power is also metallic over the whole temperature range, and the large positive value indicates that charge transport occurs with a low concentration of hole carriers. The metallic properties of this as-grown crystal are thus suggested to result from spontaneous hole-doping in the crystallization process, rather than the semi-metal electronic structure. The present study shows that artificial hole doping indeed enhances the conductivity. 相似文献
74.
The theory of relational acoustic invariance [Pickett, E. R., et al. (1999). Phonetica 56, 135-157] was tested with the Japanese stop quantity distinction in disyllables spoken at various rates. The questions were whether the perceptual boundary between the two phonemic categories of single and geminate stops is invariant across rates, and whether there is a close correspondence between the perception and production boundaries. The durational ratio of stop closure to word (where the "word" was defined as disyllables) was previously found to be an invariant parameter that classified the two categories in production, but the present study found that this ratio varied with different speaking rates in perception. However, regression and discriminant analyses of perception and production data showed that treating stop closure as a function of word duration with an intercept term represented the perception and production boundaries very well. This result indicated that the durational ratio of adjusted stop closure (i.e., closure with an added constant) to the word was invariant and distinguished the two phonemic categories clearly. Taken together, the results support the relational acoustic invariance theory, and help refine the theory with regard to exactly what form 'invariance' can take. 相似文献
75.
Cyclopropane fatty acids (CFAs) and related compounds containing CFAs commonly occur in various natural sources, including plants or microorganisms. Some CFAs exhibit intriguing biological activities such as antifungal or immunosuppressive activities. Due to their biological importance and structural features, a number of synthetic studies have been conducted to date. These total syntheses have helped to elucidate their structural determinants or biological activities. Herein the total syntheses of naturally occurring CFAs and related compounds are summarized. 相似文献
76.
The analytical performance of pyrolytic and non-pyrolytic boron nitride (PBN and NBN) platforms, attached to a commercially available graphite tube furnace, in electrothermal atomic absorption spectrometry (ETAAS) for Cd was studied. Although the tolerable pyrolysis temperature was 300 degrees C with the conventional pyrolytic graphite platform, it increased to 600 and 950 degrees C with the PBN and NBN platforms, respectively. The lifetime of the ceramic platform was 500 firings. The NBN platform provided an enhanced sensitivity with a better reproducibility than others. Using the NBN platform allowed the LOD, based on the variability of the blank (3sigma), to be 0.1 microg l(-1) within a seawater matrix (20,000 mg NaCl l(-1)) and a constant sensitivity in the range 0-30,000 mg NaCl l(-1). Good recovery in the range of 90-105% was observed for Cd (2.0 microg l(-1)) spiked into sea, estuarine and river water samples using the recommended procedure. This work proposes that using the NBN platform allows the direct monitoring and control of contaminated water for Cd by ETAAS without any chemical modification. 相似文献
77.
Zbynek Prokop Dr. Yukari Sato Dr. Jan Brezovsky Tomas Mozga Radka Chaloupkova Dr. Tana Koudelakova Petr Jerabek Veronika Stepankova Ryo Natsume Dr. Jan G. E. van Leeuwen Dick B. Janssen Prof. Jan Florian Dr. Yuji Nagata Dr. Toshiya Senda Dr. Jiri Damborsky Prof. 《Angewandte Chemie (International ed. in English)》2010,49(35):6111-6115
78.
The synthesis of immunoregulatory glycoconjugates, namely the active entity of lipopolysaccharide (LPS) from Helicobacter pylori was achieved. The results of biological activities of the LPS partial structures provide the structural basis for the immunobiological activity, especially for the immune inhibitory activity of H. pylori LPS. 相似文献
79.
80.
Toichiro A. Katsumi Katsuo Aizawa Yukari Kuroiwa Kouichi Saito Yasushi Kurata Yoshiteru Li Tetsuya Okunaka Chimori Konaka Harubumi Kato 《Photochemistry and photobiology》1996,64(4):671-675
Abstract— The authors performed photodynamic therapy (PDT), avoiding any hyperthermic effects, using a newly developed diode laser and photosensitizer, mono-L-aspar-tyl chlorin e6 (NPe6), of Meth-A fibrosarcoma implanted in mice and achieved tumor therapeutic benefit. The photodynamic light treatment was performed 5 h following the photosensitizer administration. With 5.0 mg/kg NPe6 and light doses of 50, 100, 150 and 200 J/cm2 , the tumor cure rates were 20, 50, 70 and 90%, respectively. With 100 J/cm2 laser exposure and NPe6 doses of 1.25, 2.5, 5.0, 7.5 and 10.0 mg/kg, the tumor cure rates were 0, 20, 50, 70 and 90%, respectively. A charge-coupled device (CCD) camera system was employed to measure the NPe6 fluorescence intensity correlating with the residual amount of the photosensitizer at deferent depth from the tumor surface. The ratios of the NPe6 fluorescence intensity at 3 mm from the tumor surface following 50, 100, 150 and 200 J/cm2 laser exposure to no laser exposure were 0.73, 0.36, 0.22 and 0.16, respectively. With samples sectioned at 1 mm depth, after 50 J/cm2 and the same photosensitizer dose (5 mg/kg) this ratio was 0.19. These results suggest that a certain increase in the tumor tissue level of NPe6 and a certain increase of laser light dose reaching deeper layers of tumor caused an increase in percent cure. In addition, the effectiveness of PDT depends on the total laser dose reaching deeper layers of tumors. Furthermore, the effectiveness of PDT tends to correlate with the amount of NPe6 photobleaching by PDT. 相似文献