全文获取类型
收费全文 | 1255篇 |
免费 | 38篇 |
国内免费 | 2篇 |
专业分类
化学 | 894篇 |
晶体学 | 8篇 |
力学 | 14篇 |
数学 | 39篇 |
物理学 | 340篇 |
出版年
2022年 | 13篇 |
2021年 | 8篇 |
2020年 | 8篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2016年 | 22篇 |
2015年 | 18篇 |
2014年 | 30篇 |
2013年 | 63篇 |
2012年 | 55篇 |
2011年 | 76篇 |
2010年 | 31篇 |
2009年 | 26篇 |
2008年 | 71篇 |
2007年 | 80篇 |
2006年 | 81篇 |
2005年 | 86篇 |
2004年 | 78篇 |
2003年 | 47篇 |
2002年 | 35篇 |
2001年 | 19篇 |
2000年 | 11篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1995年 | 14篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 16篇 |
1991年 | 15篇 |
1989年 | 8篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 12篇 |
1984年 | 22篇 |
1983年 | 15篇 |
1982年 | 17篇 |
1981年 | 9篇 |
1980年 | 15篇 |
1979年 | 16篇 |
1978年 | 17篇 |
1977年 | 19篇 |
1976年 | 16篇 |
1975年 | 14篇 |
1974年 | 14篇 |
1973年 | 8篇 |
1972年 | 9篇 |
1970年 | 8篇 |
1968年 | 8篇 |
排序方式: 共有1295条查询结果,搜索用时 15 毫秒
31.
Masaki Kashiwara Takahiro Kawai Toshio Oshima 《Communications in Mathematical Physics》1978,60(2):97-130
We use the holonomic character of Feynman integrals to describe their singularity structure explicitly in some simple cases. The results in §1 show that under moderate conditions Feynman amplitudes can be locally expressed essentially in terms of Legendre functions near the points where two positive- Landau-Nakanishi surfaces meet. Related topics such as hierarchical principle in perturbation theory are also discussed in terms of holonomic systems involved. In §4 we use the concrete expressions for Feynman amplitudes obtained in §1 to discuss the validity of Sato's conjecture.Supported in part by NSF MCS 75-2333Supported in part by NSF GP 36269 相似文献
32.
K. Kawai H. Maki W. Ehrlich M. Akaboshi 《Journal of Radioanalytical and Nuclear Chemistry》1989,136(1):67-74
An improved method is described for the synthesis of195mPt-radiolabelled cis-diamminedichloroplatinum/II. An amount of 10 mg of 95% enriched194Pt was irradiated for 75 h in the hydraulic conveyer of the KUR at a thermal neutron flux of approximately 8.15×1013 n.cm–2.sec–1 and the195mPt-radiolabelled CDDP was purified using HPLC. The chemical yield is 61% its chemical purity is greater than 99.74% the radiochemical purity is nearly 100%, and the specific activity is 7.4×106 Bq mg–1 CDDP/200 Ci mg–1 CDDP/. 相似文献
33.
Liang X Asanuma H Kashida H Takasu A Sakamoto T Kawai G Komiyama M 《Journal of the American Chemical Society》2003,125(52):16408-16415
Two diastereomers of a photoresponsive oligodeoxyribonucleotide tethering a trans-azobenzene, based on the chirality of the central carbon of a diol linker, were separated by reversed-phase HPLC. On the basis of 2D NMR analysis, absolute configurations of the diastereomers alpha and beta (tentatively designated from differences in their retention time) were determined as R- and S-forms, respectively. For both diastereomers, their NMR-determined duplex structure showed that trans-azobenzene intercalates between base pairs, because distinct NOEs were observed between the protons of azobenzene and those of the adjacent base pairs, such as with the imino protons and methyl protons of thymine. The melting temperatures of both duplexes were higher than that of the corresponding native duplex, which contained no azobenzene residue, due to the intercalated trans-azobenzene stabilizing the duplex by a stacking interaction. Between these two diastereomers, differences in T(m) were also found: the melting temperature of the R-form duplex (alpha-isomer) was higher than that of the S-form (beta-isomer). On the basis of the NMR-determined structure, this difference was attributed to the fact that the S-form (beta isomer) causes more stress forming the duplex than does the R-form (alpha isomer) due to disturbances of the right-hand helix. 相似文献
34.
Kenshu Fujiwara Akiyoshi Goto Daisuke Sato Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2005,46(20):3465-3468
A simple stereoselective synthesis of cis- and trans-2,3-disubstituted medium-sized cyclic ethers has been developed based on geometry-selective synthesis of 3-alkoxy-2-propenyl glycolate esters, Ireland-Claisen rearrangement of the glycolate esters, and ring-closing olefin metathesis. 相似文献
35.
H Kawai F Sakamoto M Taguchi M Kitamura M Sotomura G Tsukamoto 《Chemical & pharmaceutical bulletin》1991,39(6):1422-1425
Various 4-arylthiomethyl-2-oxo-1,3-dioxole derivatives IIIa-o were synthesized. Their hydrolysis rates by arylesterase (EC 3.1.1.2) and cholinesterase (EC 3.1.1.8) in human serum were evaluated. Some of them were not hydrolyzed by cholinesterase, but were hydrolyzed easily by arylesterase. Among the substrates, sodium 4-((5-methyl-2-oxo-1,3-dioxol-4-yl)methylthio)benzenesulfonate (IIIg) was selected for its substrate reactivity toward arylesterase and its good water solubility. In addition, neither aliesterase (EC 3.1.1.1), acetylesterase (EC 3.1.1.6) nor cholesterol esterase (EC 3.1.1.13) hydrolyzed the compound. IIIg is thus concluded to be a specific substrate for arylesterase. Our assay system for serum arylesterase using IIIg can be readily applied to an automatic analyzer in the diagnosis of liver cirrhosis. 相似文献
36.
Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1. 相似文献
37.
Summary In order to investigate the effect of the -alanine residue on the conformational stability of -helical poly(L-alanine), studies have been made on the conformations of sequential copolypeptides having the following repeating sequences: (L-Ala--Ala)
n
, (L-Ala-L-Ala--Ala)
n
, (L-Ala--Ala-L-Ala-L-Ala)
n
and (L-Ala-L-Ala-X)
n
, where X is D,L--amino-isobutyric acid residue. Conformations of these polypeptides were measured both in the solution and solid states by means of optical rotatory dispersion, infrared and far-infrared spectroscopies and X-ray diffractions. All the copolypeptides studied here did not give the -helix. It may be, therefore, concluded that the -alanine residue is not incorporated in but impairs the -helix of poly(L-alanine), since the hydrogen bond periodicity in the -helical chain is disturbed by the introduction of such a -amino acid as -alanine.With 5 figures and 2 tables 相似文献
38.
Suzumura J Hosoya N Nagao S Mitsui M Nakajima A 《The Journal of chemical physics》2004,121(6):2649-2654
We have studied the electronic structures of several gas phase exohedral lanthanide (Ln)-C(60) clusters, Ln(n)C(60) (Ln=Pr, Ho, Tb, Tm, Eu, and Yb) with n=1-4, by photoionization spectroscopy of the neutrals and photoelectron spectroscopy of their anions. Both of the spectroscopic analyses reveal that most of the Ln atoms preferably take +3 oxidation states, while Eu atoms alone assume +2 oxidation states, and that C(60) accepts up to twelve donated electrons in Ln(n)C(60). An additional photoionization examination of the oxygen atom mixing into the Ln(n)C(60) clusters demonstrated that each oxygen atom reduces two electrons from C(60). This result implies that the number of accepted electrons in C(60) can be varied by a suitable choice of the number of Ln atoms and O atoms. 相似文献
39.
Kawai K Osakada Y Takada T Fujitsuka M Majima T 《Journal of the American Chemical Society》2004,126(40):12843-12846
A series of naphthalimide (NI)- and 5-bromocytosine ((br)C)-modified oligodeoxynucleotides (ODNs) were prepared, and their lifetimes of the charge-separated states during the photosensitized one-electron oxidation of DNA were measured. Various lifetimes of the charge-separated states were observed depending on the sequence and the incorporation sites of (br)C, and the oxidation potential of G in the (br)C:G base-pair relative to that of G in the C:G base-pair and in the GGG sequence was determined by comparing the lifetimes of the charge-separated states. The change in the cytosine C5 hydrogen to bromine resulted in a 24 mV increase in the oxidation potential of G in the (br)C:G base-pair as compared to that of G in the C:G base-pair, the value of which is comparable to a 58 mV decrease in the oxidation potential of G in the GGG sequence. These results clearly demonstrate that hole transfer in DNA can be controlled through hydrogen bonding by introducing a substituent on the cytosine. 相似文献
40.
2,2[prime or minute]-3,3[double prime]-Terthiophene derivatives undergo photochemically reversible cyclization and cycloreversion reactions. The absorption peak wavelength changed systematically with substitution of the phenyl rings at 5-, 5[prime or minute]- and 5[double prime]-positions of the thiophene rings, which indicates re-routing of the [small pi]-conjugation system. 相似文献