全文获取类型
收费全文 | 582篇 |
免费 | 12篇 |
专业分类
化学 | 347篇 |
晶体学 | 2篇 |
力学 | 40篇 |
数学 | 84篇 |
物理学 | 121篇 |
出版年
2022年 | 21篇 |
2021年 | 16篇 |
2020年 | 15篇 |
2019年 | 11篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 24篇 |
2015年 | 20篇 |
2014年 | 9篇 |
2013年 | 25篇 |
2012年 | 26篇 |
2011年 | 37篇 |
2010年 | 32篇 |
2009年 | 19篇 |
2008年 | 33篇 |
2007年 | 26篇 |
2006年 | 24篇 |
2005年 | 22篇 |
2004年 | 8篇 |
2003年 | 17篇 |
2002年 | 28篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 9篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 13篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1980年 | 5篇 |
1978年 | 10篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1970年 | 3篇 |
排序方式: 共有594条查询结果,搜索用时 0 毫秒
1.
2.
Raffaele P. Bonomo Vincenzo Cucinotta Franca D' Allessandro Giuseppe Impellizzeri Giuseppe Maccarrone Enrico Rizzarelli Graziella Vecchio 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(2):167-180
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]--cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25° C andI=0.1 mol dm–3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of acis-complex trans-complex equilibrium in such systems. 相似文献
3.
4.
[graphs: see text] QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group have been performed, using the hybrid DFT functional MPW1PW91 and the 6-31G(d,p) basis set, on some representative calixarenes and on a series of simplified calixarene models allowing derivation of chemical shift surfaces versus phi and chi dihedral angles. A good reproduction of experimental data was obtained. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated. 相似文献
5.
[reaction: see text] Fmoc-protected amino acid fluorides were found to be excellent reagents for the acylation of sulfonamide safety-catch linkers (SCL) suitable for the subsequent preparation of peptide C-terminal thioesters. High loadings were obtained on different types of resins with low levels of epimerization. 相似文献
6.
G. Barone S. Capasso P. Del Vecchio C. De Sena D. Fessas C. Giancola G. Graziano P. Tramonti 《Journal of Thermal Analysis and Calorimetry》1995,45(6):1255-1264
In a previous paper, we report a preliminary DSC study on bovine (BSA) and human (HSA) serum albumins. However, at accurate HPLC analysis the commercial proteins show three peaks: Fraction V-I, probably globulins (as declared by the producers), Fraction V-II (about 15–18% of the product) and Fraction V-III that represents pure BSA or HSA. A hypothesis is that the Fraction II is a covalent dimer, or trimer or a mixture of both, generated during the scalf-life of the commercial product. Denaturation enthalpies of the purified Fraction V-III and Fraction V-II of BSA, have been determined calorimetrically, at changing thepH, and the results of both compared with those obtained on the untreated protein. Few calorimetric experiments have been also carried on a BSA monomer derivative with sulphidril group protected. Computer program have been developed for the deconvolution of exo- and endothermic effects and for the analysis of thermal denaturation profiles. 相似文献
7.
Castagnola M Rossetti DV Inzitari R Vitali A Lupi A Zuppi C Cabras T Fadda MB Petruzzelli R Giardina B Messana I 《Electrophoresis》2003,24(5):801-807
Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding. 相似文献
8.
Piero Dalla Croce Paola Del Buttero Stefano Mayorana Raffaele Vistocco 《Journal of heterocyclic chemistry》1978,15(3):515-517
Thiete 1,1-dioxide reacts with 2 moles of α-chlorobenzalphenylhydrazine and methyl phenylhydrazonochloroacetate in the presence of triethylamine leading to the pyrazole derivatives 6 and 7 whose structure and mechanism of formation are discussed. 相似文献
9.
Bonomo RP Cucinotta V Giuffrida A Impellizzeri G Magri A Pappalardo G Rizzarelli E Santoro AM Tabbi G Vagliasindi LI 《Dalton transactions (Cambridge, England : 2003)》2005,(1):150-158
An aqueous solution spectroscopic (Vis and EPR) study of the copper(II) complexes with the Ac-HGGG-NH2 and Ac-PHGGGWGQ-NH2 polypeptides (generically designated as L) suggests square base pyramids ascribable to [Cu(L)H(-2)] complex species, which contain three nitrogen donor atoms, arising from imidazole and peptide groups, in the equatorial plane and for a pseudo-octahedral geometry in the case of [CuLH-3]- and [Cu(L)H-4]2- which have four nitrogen donor atoms in their equatorial plane. The coordination sphere of the copper complex in the [Cu(L)H(-2)] species, which is present at neutral pH values, is completed by two oxygen donor atoms. ESI-MS spectra ascertained that water molecules are not present in the coordination equatorial plane of this latter species, in comparison with other copper(II) complexes with ligands bearing nitrogen and oxygen donor atoms and surely having equatorial water molecules. This indicates the coordination of a carbonyl oxygen atom in the equatorial plane has to be invoked. However, no direct proof about the involvement of a carbonyl group oxygen donor atom apically linked to copper was obtained, due to the flexibility of these structures at room temperature. Additionally, the low A(ll) value leads one to consider another oxygen atom of a carbonyl group being involved in the apical bond to copper in a fast exchange fashion. This apical interaction, which may also involve a water molecule, is more pronounced in the Cu-Ac-HGGG-NH2 than in the analogous Cu-Ac-PHGGGWGQ-NH2 system, probably because of the presence of tryptophan and proline in the polypeptide sequence. 相似文献
10.