全文获取类型
收费全文 | 1180篇 |
免费 | 8篇 |
国内免费 | 3篇 |
专业分类
化学 | 831篇 |
晶体学 | 9篇 |
力学 | 23篇 |
数学 | 120篇 |
物理学 | 208篇 |
出版年
2023年 | 4篇 |
2022年 | 13篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 12篇 |
2018年 | 7篇 |
2017年 | 8篇 |
2016年 | 7篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 42篇 |
2012年 | 59篇 |
2011年 | 88篇 |
2010年 | 54篇 |
2009年 | 37篇 |
2008年 | 91篇 |
2007年 | 71篇 |
2006年 | 70篇 |
2005年 | 78篇 |
2004年 | 57篇 |
2003年 | 63篇 |
2002年 | 37篇 |
2001年 | 20篇 |
2000年 | 14篇 |
1999年 | 13篇 |
1998年 | 8篇 |
1997年 | 20篇 |
1996年 | 16篇 |
1995年 | 17篇 |
1994年 | 11篇 |
1993年 | 17篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1985年 | 13篇 |
1984年 | 15篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 10篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有1191条查询结果,搜索用时 15 毫秒
31.
Broussy S Bernardes-Génisson V Gornitzka H Bernadou J Meunier B 《Organic & biomolecular chemistry》2005,3(4):666-669
An ortho-metallation-electrophilic substitution sequence was employed as a key step to build the 4-benzoylpyridine framework. It was found that 4-benzoylpyridine-3-carboxamide and an N-pyridyl alkylated derivative both exist in a unique cyclized hemiamidal structure, not in the usually expected keto-amide open form. These structures represent fragment models of the Isoniazid-NAD adducts involved in the mechanism of action of the antituberculous drug Isoniazid. 相似文献
32.
Volumetric heat capacities of the six binary mixtures formed from cyclopentane, cyclohexane, cycloheptane and cyclooctane were determined at 298.15 K in a Picker flow microcalorimeter. Excess heat capacities obtained from the results are compred with the temperature variation of excess enthalpies from the literature. 相似文献
33.
Jean-Luc Derocque 《Journal of mass spectrometry : JMS》1975,10(2):81-88
In the particular case where a specific ion [c]+· is generated with different internal energy, the variation of Z(E) = [(f)+]/[(c)+·] vs energy of the electron beam is discussed in relation to the P(Ei) and k(Ei) functions which describe the decay process [c]+· → [f]+. Qualitative application to seven isomeric hydrocarbons suggests that, among these isomers, two pairs might rearrange to a common intermediate before fragmentation occurs. It is found that in such cases the curves Z = f(E) for a given fragmentation are not superimposable but parallel, as suggested by theoretical considerations. 相似文献
34.
Ronald A. Buono Nathalie Kucharczyk Magrit Neuenschwander Johan Kemmink Lih-Yueh Hwang Jean-Luc Fauchère Carol A. Venanzi 《Journal of computer-aided molecular design》1996,10(3):213-232
Summary The design of enzyme mimics with therapeutic and industrial applications has interested both experimental and computational chemists for several decades. Recent advances in the computational methodology of restrained molecular dynamics, used in conjunction with data obtained from two-dimensional 1H NMR spectroscopy, make it a promising method to study peptide and protein structure and function. Several issues, however, need to be addressed in order to assess the validity of this method for its explanatory and predictive value. Among the issues addressed in this study are: the accuracy and generizability of the GROMOS peptide molecular mechanics force field; the effect of inclusion of solvent on the simulations; and the effect of different types of restraining algorithms on the computational results. The decapeptide Ser-Tyr-Ser-Met-Glu-His-Phe-Arg-Trp-Gly, which corresponds to the sequence of ACTH1–10, has been synthesized, cyclized, and studied by two-dimensional 1H NMR spectroscopy. Restrained molecular dynamics (RMD) and time-averaged restrained molecular dynamics (TARMD) simulations were carried out on four different distance-geometry starting structures in order to determine and contrast the behavior of cyclic ACTH1–10 in vacuum and in solution. For the RMD simulations, the structures did not fit the NOE data well, even at high values of the restraining potential. The TARMD simulation method, however, was able to give structures that fit the NOE data at high values of the restraining potential. In both cases, inclusion of explicit solvent molecules in the simulation had little effect on the quality of the fit, although it was found to dampen the motion of the cyclic peptide. For both simulation techniques, the number and size of the NOE violations increased as the restraining potential approached zero. This is due, presumably, to inadequacies in the force field. Additional TARMD vacuum-phase simulations, run with a larger memory length or with a larger sampling size (16 additional distance-geometry structures), yielded no significantly different results. The computed data were then analyzed to help explain the sparse NOE data and poor chymotryptic activity of the cyclic peptide. Cyclic ACTH1–10, which contains the functional moieties of the catalytic triad of chymotrypsin, was evaluated as a potential mimic of chymotrypsin by measurement of the rate of hydrolysis of esters of L-and d-phenylalanine. The poor rate of hydrolysis is attributed to the flexibility of the decapeptide, the motion of the side chains, which result in the absence of long-range NOEs, the small size of the macrocycle relative to that of the substrate, and the inappropriate orientation of the Gly, His, and Ser residues. The results demonstrate the utility of this method in computer-aided molecular design of cyclic peptides and suggest structural modifications for future work based on a larger and more rigid peptide framework. 相似文献
35.
Jean-Claude Fiaud Bernard Denner Jean-Luc Malleron 《Journal of organometallic chemistry》1985,291(3):393-402
Various mono- and di-substituted cyclopentadienes have been prepared by palladium-catalyzed alkylation of allylic esters with cyclopentadienide and t-butyl-cyclopentadienide anions. The same procedure has been applied to the preparation of substituted indenes. 相似文献
36.
A simple perturbation theory, based on the scalar wave analysis, has been used to study the propagation characteristics of radially inhomogeneous lossless fibres. The formalism has been developed with a truncated parabolic-index profile as the zero-order solution and the perturbation approach is valid for azimuthally symmetric or anti-symmetric modes near cut-off as well as far from cut-off. In addition, numerical calculations have been carried out for-profiles and have been found to be in good agreement with more rigorous calculations reported by previous authors. 相似文献
37.
Antoine Meunier Michael L. Singleton Brice Kauffmann Thierry Granier Guillaume Lautrette Yann Ferrand Ivan Huc 《Chemical science》2020,11(44):12178
As metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination spheres. We used bioinspired artificial architectures based on aromatic oligoamide foldamers to construct a rigid, modular and well-defined environment around a metal complex. Specifically, aza-aromatic monomers having a tethered [2Fe–2S] cluster have been synthesized and incorporated in conical helical foldamer sequences. Exploiting the modularity and predictability of aromatic oligoamide structures allowed for the straightforward design of a conical architecture able to sequester the metal complex in a confined environment. Even though no direct metal complex–foldamer interactions were purposely designed in this first generation model, crystallography, NMR and IR spectroscopy concurred to show that the aromatic oligoamide backbone alters the structure and fluxional processes of the metal cluster.Wrapping a [2Fe–2S] metal complex in an aromatic foldamer helix is introduced as a new approach to tailor a second coordination sphere. 相似文献
38.
Nicolas PhilippeFrançois Denivet Jean-Luc VasseJana Sopkova-de Olivera Santos Vincent Levacher Georges Dupas 《Tetrahedron》2003,59(40):8049-8056
The present report describes a stereoselective synthesis of 1,4-dihydro-4-phenyl isoquinolinones 5 based on a stereoselective Friedel-Crafts type cyclization. Cyclization precursors 1 were prepared in two steps, from the readily available (S)-mandelic acid, in 60-80% overall yield. The stereoselective electrophilic cyclization was accomplished in 20-86% yield and with 20-97% ee. In the course of this work, the presence of the amide carbonyl was found to be particularly important to guarantee a stereospecific process during the electrophilic aromatic substitution. 相似文献
39.
The parameters that influence the conformation of poly(propylene imine) dendrimers were investigated by molecular simulations using molecular mechanics and simulated annealing methods. Dendrimers with two types of peripheral units able to communicate via hydrogen bonding-amine and amide moieties-were considered in order to study the role that secondary interactions among the end groups have in the spatial organization of the dendritic branches. Radial atomic density profiles and radial atomic probability distributions were used to extract global properties, such as the degree of packing of the branches, the distribution of the monomers throughout the molecular volume, and the extent and characteristics of the surface region. Information was also obtained about the nature, location, and extent of formation of the hydrogen bonds, as well as their evolution with dendrimer generation and their assembly into networks. The analyses were supported by a detailed investigation of the first two generations, with an emphasis on the relationship between hydrogen bonding and the compactness and stability of the molecules; this allowed us to account for the generational evolution of hydrogen bonding that is experimentally observed in several poly(propylene imine) dendrimers. 相似文献
40.
Abstract— In order to investigate the interactions and the photoreactions in solution between the thymine (thy) and the psoralen (Pso) rings, we have prepared model compounds Thy-(CH2 )n -Pso in which two aromatic chromophores Thy and Pso are linked by flexible polymethylene chains of varying length (CH2 )n . Two series of compounds were examined and compared as models for the two important drugs 5-methoxypsoralen and 8-methoxypsoralen. Results concerning the 5-alkoxypsoralen series are reported here. In water, these model molecules exhibit intramolecular ring-ring stacking interactions as indicated by hypochromism in the UV and by shielding of the protons in 1 H NMR spectroscopy. These interactions disappear in organic solvents. The photochemical properties of the models were examined in relation with their ground state interaction properties. Irradiation at 365 nm carried out at the usual concentrations (10-2 -10-3 M) leads exclusively to a stereoselective dimerization involving the psoralen moieties of the models at the 3,4 double bonds. However, when operating at exceedingly low concentrations (2 × 10-5 M ), the psoralen photodimerization is avoided and a highly regio and stereo-selective psoralen thymine photoaddition is observed involving the 3,4 double bond of psoralen leading to the cis adduct. The same reaction occurs for all models under study being independent of the length of the (CH2 )n polymethylene linking chain, n = 2 to 6, 12 and of the solvent used. This is unambiguous proof for the highest intrinsic photoreactivity of the 3,4 vs the 4',5' double bond in 5-alkoxy psoralen. 相似文献