全文获取类型
收费全文 | 1517篇 |
免费 | 28篇 |
国内免费 | 7篇 |
专业分类
化学 | 1163篇 |
晶体学 | 7篇 |
力学 | 21篇 |
数学 | 116篇 |
物理学 | 245篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 9篇 |
2020年 | 17篇 |
2019年 | 11篇 |
2018年 | 17篇 |
2017年 | 13篇 |
2016年 | 29篇 |
2015年 | 22篇 |
2014年 | 36篇 |
2013年 | 77篇 |
2012年 | 86篇 |
2011年 | 120篇 |
2010年 | 54篇 |
2009年 | 73篇 |
2008年 | 73篇 |
2007年 | 91篇 |
2006年 | 104篇 |
2005年 | 80篇 |
2004年 | 71篇 |
2003年 | 73篇 |
2002年 | 74篇 |
2001年 | 18篇 |
2000年 | 33篇 |
1999年 | 24篇 |
1998年 | 22篇 |
1997年 | 22篇 |
1996年 | 18篇 |
1995年 | 11篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1983年 | 11篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 11篇 |
1979年 | 18篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1974年 | 5篇 |
1971年 | 6篇 |
1968年 | 4篇 |
排序方式: 共有1552条查询结果,搜索用时 15 毫秒
31.
Kenjiro Hattori Akira Kenmoku Tsukasa Mizuguchi Daisuke Ikeda Mamoru Mizuno Toshiyuki Inazu 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(1-2):9-16
A synthetic series of heptakis-galactose-branched cyclodextrins (termed CDs) having a longer spacer arm using two amino-caproic acids as an enlarging unit were prepared. Starting with heptakis-amino-β-CD or heptakis-amino-caproic-amide-β-CD, treated with galactosyl-glucono-amide-caproic acid, the new compounds heptakis (Gal-cap1)-CD (4) or heptakis (Gal-cap2)-CD (5) were obtained. The longer galactose spacer arm extremely favors the PNA association. The effect of branch length on K with PNA was enhanced up to 138-fold 3 as well as with DXR enhanced up to 81-fold. Hexakis (Gal-cap2)-CD (6) was prepared and the association constants with rat liver cells were observed to be 2.5 × 1010 M−1. A multi-high mannose type oligosaccharide branched CD (7) showed a large association constant with DXR up to 1.1 × 109 M−1. The two-dimensional map for the association constants of newly synthesized oligosaccharide-branched CDs toward lectin or liver cells versus the association constants toward a drug (doxorubicin) suggested a method of finding a better targeting drug carrier. The structural effect of the oligosaccharide-CDs showed that the number and length of the branch were dominant factors in designing for enhanced dual recognition. 相似文献
32.
Nabeshima T Saiki T Iwabuchi J Akine S 《Journal of the American Chemical Society》2005,127(15):5507-5511
Synthesis and binding behavior of a novel multi-responsive host 1, in which two esters, two polyether moieties, two urea sites, and two bipyridine units as ion binding sites are arranged on the calix[4]arene skeleton, is reported. 1 recognizes Na(+) and Ag(+) simultaneously and quantitatively and captures an anionic guest. The ability of 1 to recognize anions, including CF(3)SO(3)(-) and BF(4)(-), remarkably increases in a stepwise manner using Na(+) and Ag(+) as effectors. The enhancement of the K(a) eventually reaches factors of 1500 and 2000 for NO(3)(-) and CF(3)SO(3)(-), respectively, in the presence of both Na(+) and Ag(+), compared to the free 1. The regulation of binding of multiple ligands may be applicable to multistep cascade systems for the amplification of molecular events, and further studies in this field could provide insight applicable to more advanced molecular devices. 相似文献
33.
Yoshiyuki Koyama Kazunari Harima Kei Matsuzaki Toshiyuki Uryu 《Journal of polymer science. Part A, Polymer chemistry》1985,23(12):2989-2998
1,4-Anhydro-2,3-di-O-benzyl-α-L -arabinopyranose (=1,5-anhydro-2,3-di-O-benzyl-β-L -arabinofuranose) (ABAP) was synthesized and underwent cationic ring-opening polymerization with several kinds of Lewis acids. All the polylmers prepared by Lewis acids as catalyst were found to consist of two different structural units, α-furanosidic and β-furanosidic units, and the structure of the polymers greatly depended on the polymerization conditions. Polymerization of ABAP with antimony pentachloride catalyst at 0°C for 42 h gave a polymer with the highest α content of 93%, and that at ?20°C for 3 h gave a polymer with the lowest (25%) α content. The other catalysts such as phosphorus pentafluoride, boron trifluoride etherate, niobium pentafluoride, and tantalum pentafluoride also afforded polymers with mixed structure of α-and β-furanosides. After debenzylation of poly(ABAP), a new polysaccharide, L -arabinofuranan was obtained. 相似文献
34.
Yuji Minoura Hisashi Hironaka Toshiyuki Kasabo Yukio Ueno 《Journal of polymer science. Part A, Polymer chemistry》1969,7(11):3245-3255
Reaction of poly(vinyl chloride) with magnesium under various conditions was attempted, but poly(vinyl chloride) did not react with magnesium. The reactions of poly(vinyl chloride) with benzylmagnesium chloride and allylmagnesium chloride as Grignard reagents were carried out in tetrahydrofuran at reflux temperature. It was found that the chlorine atoms in the poly(vinyl chloride) were replaced by benzyl and allyl groups by the coupling reaction, and a small amount of Grignard reagent of poly(vinyl chloride) was formed by the magnesium–halogen exchange reaction. The extent of the substitution increased with increasing reaction time and concentration of the Grignard reagent. 相似文献
35.
36.
K. Miyagai K. Taga T. Yoshida H. Okabayashi E. Nishio 《Colloid and polymer science》1991,269(2):153-160
Barium ethyl(alkyl)phosphates, as new simple surfactants ((C2H5O)(RO)-PO
2
–
)2Ba2+ with various chain length ofR, were synthesized. The infrared spectra in the CH stretching region were measured for these surfactants in the solid state and in aqueous solution, and assignments were made. In particular, the ordering and environment of octyl chains in the different phases of the barium ethyl(octyl)phosphate-water system were studied by the Fourier-transform-infrared and Raman spectra. The CH stretching bands in the infrared spectra reflected the ordering and environment of octyl chains in each phase. The Raman band connected to the PO
2
–
symmetric stretching mode was sensitively shifted. This was caused by the change of aggregation structures with different Ba2+...PO
2
–
interaction. The infrared band arising from the PO
2
–
antisymmetric stretching mode was insensitive to the phase structures. The C–C stretching region in the infrared spectra was used to discuss the ordering of each phase. 相似文献
37.
Kohara T Koyama T Fujimura M Tanaka H Maeda J Fujimoto T Yamamoto I Arita M 《Chemical & pharmaceutical bulletin》2002,50(6):818-821
The oxidation behavior of Y-931, a potent atypical antipsychotic drug, was compared with that of clozapine and olanzapine. In two enzymatic systems (horseradish peroxidase (HRP)/glutathione (GSH) and HRP/H(2)O(2)/GSH) which generate thiyl radicals, clozapine markedly strengthened the electron paramagnetic resonance (EPR) signal for the radical. Olanzapine, Y-931 and the major metabolites (compounds 1-3) had no or minimal effect on the intensity of this signal. In addition, the redox potential values for the three derivatives were in accord with the EPR spin trapping results. In toxicological experiments in human leukocytes, a concentration-dependent toxicity was observed when neutrophils were incubated with clozapine (1-10 micromol/l) and H(2)O(2) (1 mmol/l). However, Y-931 and olanzapine did not show remarkable toxicity under the conditions. 相似文献
38.
Reiji Tanaka Yu Kurishiba Hideo Miyake Toshiyuki Shibata 《Molecules (Basel, Switzerland)》2022,27(11)
In this study, we aimed to isolate bacteria capable of degrading the polysaccharide ulvan from the green algae Ulva sp. (Chlorophyta, Ulvales, Ulvaceae) in marine environments. We isolated 13 ulvan-degrading bacteria and observed high diversity at the genus level. Further, the genera Paraglaciecola, Vibrio, Echinicola, and Algibacter, which can degrade ulvan, were successfully isolated for the first time from marine environments. Among the 13 isolates, only one isolate (Echinicola sp.) showed the ability not only to produce externally expressed ulvan lyase, but also to be periplasmic or on the cell surface. From the results of the full-genome analysis, lyase was presumed to be a member of the PL25 (BNR4) family of ulvan lyases, and the bacterium also contained the sequence for glycoside hydrolase (GH43, GH78 and GH88), which is characteristic of other ulvan-degrading bacteria. Notably, this bacterium has a unique ulvan lyase gene not previously reported. 相似文献
39.
Toshiyuki Moriuchi Toshikazu Hirao 《Journal of inclusion phenomena and macrocyclic chemistry》2012,74(1-4):23-40
This review describes an outline of dipeptide-induced chirality organization by using molecular scaffolds. A variety of ferrocene-dipeptide conjugates as bioorganometallics are designed to induce chirality-organized structures of peptides. The ferrocene serves as a reliable organometallic scaffold with a central reverse-turn unit for the construction of protein secondary structures via intramolecular hydrogen bondings, wherein the attached dipeptide strands are constrained within the appropriate dimensions. Another interesting feature of ferrocene-dipeptide conjugates is their strong tendency to self-assemble through contribution of available hydrogen bonding sites for helical architectures in solid states. Symmetrical introduction of two dipeptide chains into a urea molecular scaffold is performed to induce the formation of the chiral hydrogen-bonded duplex, wherein each hydrogen-bonded duplex is connected by continuous intermolecular hydrogen bonds to form a double helix-like arrangement. 相似文献
40.
Sun-Chan Jeong Ichiro Katayama Hirokane Kawakami Yutaka Watanabe Hironobu Ishiyama Nobuaki Imai Yoshikazu Hirayama Hiroari Miyatake Masao Sataka Hiroyuki Sugai Satoru Okayasu Shin-Ichi Ichikawa Katsuhisa Nishio Shinichi Mitsuoka Takamitsu Nakanoya Takashi Hashimoto Takanori Hashimoto Masahito Yahagi 《Solid State Ionics》2009,180(6-8):626-630
The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of 8Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects. 相似文献