全文获取类型
收费全文 | 2413篇 |
免费 | 610篇 |
国内免费 | 98篇 |
专业分类
化学 | 2970篇 |
晶体学 | 17篇 |
力学 | 1篇 |
综合类 | 3篇 |
数学 | 4篇 |
物理学 | 126篇 |
出版年
2024年 | 2篇 |
2023年 | 48篇 |
2022年 | 59篇 |
2021年 | 79篇 |
2020年 | 172篇 |
2019年 | 89篇 |
2018年 | 105篇 |
2017年 | 60篇 |
2016年 | 187篇 |
2015年 | 209篇 |
2014年 | 191篇 |
2013年 | 284篇 |
2012年 | 176篇 |
2011年 | 229篇 |
2010年 | 172篇 |
2009年 | 141篇 |
2008年 | 156篇 |
2007年 | 126篇 |
2006年 | 103篇 |
2005年 | 71篇 |
2004年 | 81篇 |
2003年 | 72篇 |
2002年 | 44篇 |
2001年 | 23篇 |
2000年 | 30篇 |
1999年 | 24篇 |
1998年 | 39篇 |
1997年 | 39篇 |
1996年 | 21篇 |
1995年 | 15篇 |
1994年 | 21篇 |
1993年 | 13篇 |
1992年 | 10篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有3121条查询结果,搜索用时 15 毫秒
31.
Naringenin is a natural widespread flavanone occurring in different foodstuffs that presents several important biological activities. Although its properties are well documented, its mechanisms of action are still controversial. The present article reports a conformational analysis of naringenin, using the semiempirical AM1 and ab initio methods, at the Hartree–Fock level of theory. The 3-21G, 3-21G*, 6-31G, and 6-31G** basis sets were used. The electron correlation effects were included through the Møller–Plesset second-order perturbation theory. The solvation of naringenin has been investigated through the standard SCRF, the supermolecule (SM), and the combined SM/SCRF models. The results have shown that there are two degenerate forms of naringenin, differing mainly by the orientation of a hydroxyl group (C4—OH). The energy barrier for the interconversion between them is ca. 6 kcal.mol–1, suggesting some conjugation between the -system of the aromatic B ring and the hydroxyl group (C4—OH). 相似文献
32.
Gerhard BringmannStefan Busemann 《Tetrahedron》2003,59(8):1245-1253
The first quantum chemical calculation of the circular dichroism (CD) spectra of michellamines has been achieved, based on a complete quantum chemical conformational analysis. Michellamines are dimeric naphthylisoquinoline alkaloids and thus naturally occurring quateraryls, with a large molecular size and flexibility and equipped with stereogenic centers and axes. 相似文献
33.
In the golden age of organocatalysis 总被引:8,自引:0,他引:8
The term "organocatalysis" describes the acceleration of chemical reactions through the addition of a substoichiometric quantity of an organic compound. The interest in this field has increased spectacularly in the last few years as result of both the novelty of the concept and, more importantly, the fact that the efficiency and selectivity of many organocatalytic reactions meet the standards of established organic reactions. Organocatalytic reactions are becoming powerful tools in the construction of complex molecular skeletons. The diverse examples show that in recent years organocatalysis has developed within organic chemistry into its own subdiscipline, whose "Golden Age" has already dawned. 相似文献
34.
The conformational change of the 39-43 residues of the amyloid beta-peptide (Abeta) toward a beta-sheet enriched state promotes self-aggregation of the peptide molecules and constitutes the major peptide component of the amyloid plaques in Alzheimer patients. The crucial question behind the self-aggregation of Abeta is related to the different pathways the peptide may take after cleavage from the amyloid precursor proteins at cellular membranes. This work is aiming at determining the conformation of the Abeta (1-40) adsorbed on hydrophobic Teflon and hydrophilic silica particles, as model sorbent surfaces mimicking the apolar transmembrane environment and the polar, charged membrane surface, respectively. The mechanism by which the Abeta interacts with solid surfaces strongly depends on the hydrophobic/hydrophilic character of the particles. Hydrophobic and electrostatic interactions contribute differently in each case, causing a completely different conformational change of the adsorbed molecules on the two surfaces. When hydrophobic interactions between the peptide and the sorbent prevail, the adsorbed Abeta (1-40) mainly adopts an alpha-helix conformation due to H-bonding in the apolar part of the peptide that is oriented towards the surface. On the other hand, when the peptide adsorbs by electrostatic interactions beta-sheet formation is promoted due to intermolecular association between the apolar parts of the adsorbed peptide. Irrespective of the characteristics of the solid sorbent, crowding the surface results in intermolecular association between adsorbed molecules leading to a strong aggregation tendency of the Abeta (1-40). [Diagram: see text] CD spectra of Abeta (1-40) at pH 7: A) in solution ([Abeta]=0.2 mg.ml(-1)) freshly prepared (line) and after overnight incubation (symbols);B) on Teflon (Gamma=0.5 mg.m(-2)). 相似文献
35.
Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献
36.
Zheng-Ping Yi Jun Hu Hui-Lan Chen 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(1-2):1-8
Conformational analysis of inclusion complexes of sodium 3-hydroxy-2-naphthalenecarboxylate with -cyclodextrin and heptakis-(2,3,6-tri-o-methyl)--cyclodextrin in D2O was investigated by 1D and 2D 1HNMR measurements. The results show that part of the naphthyl group of sodium 3-hydroxy-2-naphthalenecarboxylate is situated in the 2,3-OH side of the -cyclodextrin cavity asymmetrically while the whole naphthyl group is included in the heptakis-(2,3,6-tri-o-methyl)--cyclodextrin cavity with the caboxylate and hydroxy group close to the 6-OCH3 group. 相似文献
37.
We measured FT-IR spectra of intact Acholeplasma laidlawii cells grown at 37 °C on palmitic acid (C16:0) or on binary palmitic acid-d31/oleic acid (C16:0-d31/C18:1(9)) at an initial mole ratio of 2:3, which have been previously reported to produce significant fluctuations in CH2 symmetric stretching (νsCH2) and CD2 asymmetric stretching (νaCD2) frequencies (Biochim. Biophys. Acta 1279 (1996) 49). Time courses for acyl chain νsCH2 and νaCD2 frequencies determined from fourth derivative spectra are presented. Fluctuations were detected with the C16:0 enriched cells at temperatures above 40 °C as well as with the cells enriched in 2:3 C16:0-d31/C18:1(9). These observations at temperatures above 40 °C for the C16:0 enriched cells were not in agreement with the conclusion in the previous work by Moore et al. Our results have suggested that the 2850 cm−1 νsCH2 band comprises two components arising from trans and gauche conformations, and that the fluctuations in νsCH2 frequency are caused by random temporal changes in the relative intensities of these two components. 相似文献
38.
Ruta Bariseviciute Justinas Ceponkus Alytis Gruodis Valdas Sablinskas 《Central European Journal of Chemistry》2006,4(4):578-591
Ozonization reaction of simple alkenes was studied by means of FT infrared absorption gas spectroscopy. The reaction was performed
at 95 K in neat films of the reactants. IR absorption spectra of the gaseous products were recorded. The spectra were analyzed
combining experimental results with theoretical calculations performed at B3LYP 6-311++G (3df, 3pd) level. We found that among
all theoretically predicted conformers of propene secondary ozonide, only one which has the O-O half-chair configuration for
the five membered ring and the radical attached in the equatorial position was present in the sample. Samples of 1-butene and 1-heptene secondary ozonides consist from two conformers of very
similar energy (ΔH=0.3 kJ/mol). The most stable conformer for both ozonides is the one with O-O half-chair configuration of the five membered
ring and the radical attached in equatorial position and the aliphatic chain in gauche position. The second stable conformer has the aliphatic chain in anti position. 相似文献
39.
Ronova I. A. Eylshina L. B. Vasilyuk A. N. Rusanov A. L. Bulycheva E. G. 《Russian Chemical Bulletin》2002,51(5):820-824
The dependence of the glass transition and initial decomposition temperatures of polyperyleneimide and polynaphthylimide on the conformational rigidity was studied by the Monte Carlo, Kuhn segment, and quantum chemical AM1 methods. The corresponding linear plots can be used for estimation of the glass transition and initial decomposition temperatures when experimental determination is difficult. 相似文献
40.
The SIBFA procedure (Sum of Interactions Between Fragments computedAb initio, Ref [1]) is extended to the study of the conformational behavior of representative molecules containing amide nitrogens and carbonyl and carboxylate oxygens. The molecules studied are C- and N-ethylammonium formamide, C- and N-ethanol-formamide, ethylammonium formate and ethanolformate. The cases investigated include interactions of the types which occur between functional groups in proteins or ionophores. The accuracy of the procedure, assessed by comparing the results to those of correspondingab initio SCF computations, is very satisfactory. An application of the procedure to study the conformation of the glycyl and alanyl dipeptides as a function of the backbone torsional angles and is presented. 相似文献