全文获取类型
收费全文 | 1777篇 |
免费 | 67篇 |
国内免费 | 5篇 |
专业分类
化学 | 1262篇 |
晶体学 | 29篇 |
力学 | 14篇 |
综合类 | 1篇 |
数学 | 103篇 |
物理学 | 440篇 |
出版年
2023年 | 12篇 |
2022年 | 6篇 |
2021年 | 23篇 |
2020年 | 16篇 |
2019年 | 29篇 |
2018年 | 19篇 |
2017年 | 12篇 |
2016年 | 32篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 85篇 |
2012年 | 92篇 |
2011年 | 86篇 |
2010年 | 56篇 |
2009年 | 56篇 |
2008年 | 106篇 |
2007年 | 125篇 |
2006年 | 120篇 |
2005年 | 114篇 |
2004年 | 114篇 |
2003年 | 83篇 |
2002年 | 72篇 |
2001年 | 46篇 |
2000年 | 47篇 |
1999年 | 29篇 |
1998年 | 23篇 |
1997年 | 21篇 |
1996年 | 24篇 |
1995年 | 22篇 |
1994年 | 19篇 |
1993年 | 17篇 |
1992年 | 19篇 |
1991年 | 13篇 |
1990年 | 14篇 |
1989年 | 8篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 25篇 |
1984年 | 27篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 15篇 |
1978年 | 5篇 |
1977年 | 12篇 |
1975年 | 11篇 |
1974年 | 9篇 |
1972年 | 7篇 |
排序方式: 共有1849条查询结果,搜索用时 15 毫秒
51.
Koga T Taguchi K Kinoshita T Higuchi M 《Chemical communications (Cambridge, England)》2002,(3):242-243
A novel artificial protein with simple primary structure, poly(gamma-methyl-L-glutamate)-grafted polyallylamine, has been prepared and the resultant peptide has shown a unique property of pH-regulated conformation and morphology. 相似文献
52.
53.
Tomoyuki Esumi 《Tetrahedron letters》2004,45(37):6941-6945
Isoplagiochin D, a highly strained macrocyclic bis(bibenzyls) with two biaryl units isolated from the liverwort Pladiochila fruticosa, was prepared in 10.6% overall yield for the 11 steps by an efficient synthetic approach involving the construction of two bibenzyl and one biaryl units using Horner-Wadsworth-Emmons and Suzuki-Miyaura protocols. 相似文献
54.
55.
Kyoichiro Shibatani Yuzuru Fujiwara Kiyoshi Fujii 《Journal of polymer science. Part A, Polymer chemistry》1970,8(7):1693-1703
High-resolution proton magnetic resonance and infrared spectra of poly(vinyl formal) were studied in comparison with those of the model formals obtained from stereoisomers of pentane-2,4-diol and heptane-2,4,6-triol in order to learn spectral changes due to differences of the steric structures of the polymer. In the NMR spectrum of transformal obtained from dl diol or dl,dl (syndiotactic) triol, all proton signals were well interpreted by assuming a rapid chair-chair inversion of the formal ring. On the other hand, no such inversion was observed spectroscopically in cis-formal obtained from the meso diol or meso,meso (isotactic) triol, and the cis-formal ring was supposed to take a diequatorial form preferentially. Consequently, dioxymethylene protons gave a single peak (equivalent) in trans-formal and an AB quartet (nonequivalent) in cis-formal. In the spectra of poly(vinyl formal), the dioxymethylene signal was an overlap of the singlet and quartet in dimethylsulfoxide solution. Observations of the spectra of various poly(vinyl formals) obtained from poly(vinyl alcohols) of different tacticities and study of temperature dependence of the signal have shown that the singlet and quartet are attributed to trans- and cis- formals, respectively, in the polymer spectrum also. In the infrared spectra of poly(vinyl formals), the 800 and 785 cm-1 bands were found to be related to cis- and trans-formal rings respectively. A linear relationship was confirmed between D785/D800 and trans/cis ratios determined from the peak intensities of the dioxymethylene proton signals. 相似文献
56.
Takaki K Itono Y Nagafuji A Naito Y Shishido T Takehira K Makioka Y Taniguchi Y Fujiwara Y 《The Journal of organic chemistry》2000,65(2):475-481
Three-component coupling of acylphosphonates and two carbonyl compounds leading to beta-hydroxyphosphonates has been achieved with low-valent samariums. Thus, acylphosphonates reacted with aldehydes in the presence of semicatalytic amounts of samarium metal or SmI(2) to give acyloxyphosphonates in good yields. The second coupling reaction of the acyloxyphosphonates with aldehydes or ketones promoted by SmI(2) afforded beta-hydroxyphosphonates instead of olefins. Moreover, these two reactions could be carried out in one pot. 相似文献
57.
Octadecapeptides carrying a ferrocene moiety at the molecular terminal were self-assembled on gold, and long-range electron transfer from the ferrocene moiety to gold was investigated by electrochemical methods. Effects on electron transfer of dipole moment of helical peptides, linkers connecting the peptide to gold, and chromophores introduced into the side chains were discussed. Cyclic voltammetry of the monolayers in an aqueous solution revealed that long-range electron transfer over 40 A occurred along the peptide molecule. Chronoamperometry showed that the long-range electron transfer should be ascribed to a hopping mechanism with use of amide groups as hopping sites. Electron transfer through the long peptide was not significantly accelerated by the dipole moment. However, the linker remarkably affected electron transfer depending on whether it was a methylene chain or a phenylene group, suggesting that local electron transfer between gold and the peptides should be the slowest step to determine the overall rate. Pyrenyl groups introduced into the side chains in the middle of the peptide molecule did not noticeably change electron transfer, probably because pyrenyl groups were too distant to allow direct electron transfer between them. Electrostatic potential profiles across the peptide monolayers were also calculated to explain reasonably the several interesting features in the present peptide systems. 相似文献
58.
Evaluation of the adsorption affinity of proteins to calcium hydroxyapatites by desorption and pre-adsorption methods 总被引:1,自引:0,他引:1
Kazuhiko Kandori Aya Fujiwara Megumi Mukai Akemi Yasukawa Tatsuo Ishikawa 《Colloids and surfaces. B, Biointerfaces》1998,11(6):313-320
The adsorption affinity of bovine serum albumin (BSA) and lysozyme (LSZ) to calcium hydroxyapatite (CaHAP) was evaluated by desorption and two step adsorption methods. These experiments were carried out at 15°C in a 1×10−4 mol dm−3 KCl solution of pH 6.0. BSA molecules were scarcely desorbed, exhibiting an irreversible adsorption of BSA, though LSZ slightly desorbed. This result supports our previous findings that LSZ adsorbs weakly onto phosphate ions exposed on ac or bc faces of CaHAP while BSA adsorbs strongly onto positively charged sites on ac or bc faces of CaHAP. The amount of adsorbed LSZ was markedly increased by the pre-adsorption of BSA, where LSZ was adsorbed onto BSA-covered CaHAP. On the other hand, the amount of adsorbed BSA was not changed by the pre-adsorption of LSZ. In both pre-adsorption systems it was confirmed by an HPLC method that no protein molecule pre-adsorbed was desorbed after the post-adsorption procedure. Therefore, it was interpreted that the enhancement of adsorption of positively charged LSZ is induced by an electrostatic attractive force through pre-adsorption of negatively charged BSA molecules with a high coverage. However, since the coverage of LSZ onto CaHAP is considerably low, no stimulation of BSA adsorption occurred on the LSZ-covered surface. The formation of double protein adsorbed layers consisting of pre- and post-adsorbed proteins was proposed. 相似文献
59.
Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state. 相似文献
60.
Keisuke Kato Chie Matsuba Hiroyuki Takayama Tomoyuki Mochida Tat'yana A. Peganova Oleg V. Gusev 《Tetrahedron》2006,62(42):9988-9999
The oxidative cyclization-carbonylation of meso-2-alkyl-2-propargylcyclohexane-1,3-diols mediated by Pd(II) with chiral bisoxazoline (box ligand) afforded bicyclic-β-alkoxyacrylates. Based on a ligand screening, 2,2′-isopropylidenebis[(4S,5R)-4,5-di(2-naphthyl)-2-oxazoline] ligand has been developed. The products with a chiral quaternary carbon were obtained in 71-100% yields with 85-95% ee. 相似文献