全文获取类型
收费全文 | 1349篇 |
免费 | 37篇 |
国内免费 | 3篇 |
专业分类
化学 | 1038篇 |
晶体学 | 10篇 |
力学 | 15篇 |
综合类 | 1篇 |
数学 | 37篇 |
物理学 | 288篇 |
出版年
2022年 | 14篇 |
2021年 | 18篇 |
2020年 | 25篇 |
2019年 | 23篇 |
2018年 | 11篇 |
2016年 | 21篇 |
2015年 | 13篇 |
2014年 | 29篇 |
2013年 | 62篇 |
2012年 | 80篇 |
2011年 | 60篇 |
2010年 | 37篇 |
2009年 | 30篇 |
2008年 | 68篇 |
2007年 | 74篇 |
2006年 | 86篇 |
2005年 | 82篇 |
2004年 | 68篇 |
2003年 | 54篇 |
2002年 | 64篇 |
2001年 | 33篇 |
2000年 | 37篇 |
1999年 | 30篇 |
1998年 | 20篇 |
1997年 | 14篇 |
1996年 | 18篇 |
1995年 | 16篇 |
1994年 | 19篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 11篇 |
1990年 | 15篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 6篇 |
1985年 | 20篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1980年 | 13篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 13篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 19篇 |
1967年 | 5篇 |
排序方式: 共有1389条查询结果,搜索用时 31 毫秒
31.
Jun-Ichi Kikuchi Yukito Murakami 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(2-3):209-221
Steroid cyclophanes, bearing four bile acid moieties covalently placed on a tetraazaparacyclophane skeleton, were designed and synthesized as artificial cell-surface receptors. Guest-binding behavior of the steroid cyclophanes embedded in a bilayer membrane formed with a synthetic peptide lipid was clarified by means of fluorescence and circular dichroism spectroscopy. We found that the steroid cyclophane effectively bound aromatic guests in both bilayer membranes and aqueous solution. In addition, copper(II) ions acted as a guest species for the steroid cyclophane and a competitive inhibitor toward a NADH-dependent lactate dehydrogenase (LDH). On these grounds, we constituted a supramolecular assembly as an artificial signaling system in combination with the steroid cyclophane, a cationic peptide lipid, and LDH. As a consequence, the steroid cyclophane acted as an effective artificial cell-surface receptor being capable of transmitting an external signal to the enzyme in collaboration with copper(II) ions as a signal transmitter. 相似文献
32.
1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens… 相似文献
33.
To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization
of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium
persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration
compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization.
Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was
observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the
end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles.
From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion
radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA.
Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen
abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen
abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical
to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of
hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Received: 26 April 2001 Accepted: 6 September 2001 相似文献
34.
[reaction: see text] AgPF6-promoted oxidation of 5,10,15-trialkyl zinc(II) porphyrins led to formation of meso-meso linked diporphyrins, which were further oxidized with Sc(OTf)3 and DDQ to give meso-meso, beta-beta, beta-beta triply linked diporphyrins that exhibited a stronger aggregation propensity than corresponding meso-aryl diporphyrins. 相似文献
35.
K. Kaya K. Fuke S. Nonose N. Kikuchi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1989,12(1-4):571-573
Aluminum clusters were generated by a laser vaporization method. Ionization potential of Al2 was found to be lower than that of Al. In the reaction with oxygen at high concentration, the mixed cluster Al9O7 survives predominantly as a stable cluster. Ammonia was found to be adsorbed weakly on the Aln surface. 相似文献
36.
Takeshi Kikuchi George Nmethy Harold A. Scheraga 《Journal of computational chemistry》1989,10(3):287-294
The method presented earlier [T. Kikuchi, G. Némethy, and H.A. Scheraga, (1986) J. Comput. Chem. 7 , 67] for the classification of patterns of the three-dimensional folding of a covalently crosslinked polypeptide chain has been extended to nonplanar proteins. The procedure described earlier was applicable only to proteins termed planar, i.e., with a connexity of the crosslinks (e.g., disulfide bonds) that can be represented in a planar diagram. The procedure described in the present work is applicable to any (planar or nonplanar) pattern of crosslinking. The classification is based on a systematic and objective method of enumeration of spatial geometric arrangements of loops (SGAL) using no information other than the location of the disulfide bonds in the amino acid sequence. Various SGAL classes correspond to the presence of different ways of mutual penetration of loops, called thrustings and entanglements. Information on SGAL classes can be of use in structural predictions of folding patterns of proteins. 相似文献
37.
Kikuchi H Saito Y Komiya J Takaya Y Honma S Nakahata N Ito A Oshima Y 《The Journal of organic chemistry》2001,66(21):6982-6987
We investigated the constituents of Dictyostelium discoideum to clarify the diversity of secondary metabolites of Dictyostelium cellular slime molds and to explore biologically active substances that could be useful in the development of novel drugs. From a methanol extract of the multicellular fruit body of D. discoideum, we isolated two novel amino sugar analogues, furanodictine A (1) and B (2). They are the first 3,6-anhydrosugars to be isolated from natural sources. Their relative structures were elucidated by spectral means, and the absolute configurations were confirmed by asymmetric syntheses of 1 and 2. These furanodictines potently induce neuronal differentiation of rat pheochromocytoma (PC-12) cells. 相似文献
38.
Design, synthesis, and binding affinities of pyrrolinone-based somatostatin mimetics 总被引:1,自引:0,他引:1
Smith AB Charnley AK Mesaros EF Kikuchi O Wang W Benowitz A Chu CL Feng JJ Chen KH Lin A Cheng FC Taylor L Hirschmann R 《Organic letters》2005,7(3):399-402
[structure: see text] Tetrapyrrolinone somatostatin (SRIF) mimetics (cf. 1), based on a heterochiral (D,L-mixed) pyrrolinone scaffold, were designed, synthesized, and evaluated for biological activity. The iterative synthetic sequence, incorporating the requisite functionalized coded and noncoded amino acid side chains, comprised a longest linear synthetic sequence of 23 steps. Binding affinities at two somatostatin receptor subtypes (hsst 4 and 5) reveal micromolar activity, demonstrating that the d,l-mixed pyrrolinone scaffold can be employed to generate functional mimetics of peptide beta-turns. 相似文献
39.
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
40.