全文获取类型
收费全文 | 348篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 274篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 55篇 |
物理学 | 24篇 |
出版年
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 23篇 |
2020年 | 12篇 |
2019年 | 11篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 11篇 |
2015年 | 6篇 |
2014年 | 9篇 |
2013年 | 14篇 |
2012年 | 36篇 |
2011年 | 28篇 |
2010年 | 14篇 |
2009年 | 13篇 |
2008年 | 22篇 |
2007年 | 22篇 |
2006年 | 11篇 |
2005年 | 17篇 |
2004年 | 14篇 |
2003年 | 13篇 |
2002年 | 7篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1978年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有359条查询结果,搜索用时 15 毫秒
11.
The conformational behavior of the title compounds has been investigated by Hartree-Fock, MP2, and DFT computations on the most significant structures related to variations of the backbone dihedral angles, cis/trans isomerism around the peptide bond, and diastereoisomeric puckering of the pyrrolidine ring. In vacuum the reversed gamma turn (gammal), characterized by an intramolecular hydrogen bridge, corresponds to the absolute energy minimum for both puckerings (up and down) of the pyrrolidine ring. An additional energy minimum is found in the helix region, but only for an up puckering of the pyrrolidine ring. When solvent effects are included by means of the polarizable continuum model the conformer observed experimentally in condensed phases becomes the absolute minimum. The down puckering is always favored over its up counterpart, albeit by different amounts (0.4-0.5 kcal/mol for helical structures and about 2 kcal/mol for gammal structures). In helical structures cis arrangements of the peptide bond are only slightly less stable than their trans counterparts. This is no longer true for gammal structures, because the formation of an intramolecular hydrogen bond is possible only for trans peptide bonds. In most cases, proline and hydroxyproline show the same general trends; however, the electronegative 4(R) substituent of hydroxyproline leads to a strong preference for up puckerings irrespective of the backbone conformation. 相似文献
12.
Caterina Sartori 《manuscripta mathematica》1982,38(2):225-238
We present an asymptotic analysis for the solution of period 4 of
, where f is an odd function and a positive parameter.This work was supported by a C.N.R. fellowship during the period in which the author was visiting Rutgers University. 相似文献
13.
Chakravarthi Simhadri Liting Bi Mathieu L. Lepage Mahdi Takaffoli Zhipeng Pei Stefania F. Musolino Abbas S. Milani Gino A. DiLabio Jeremy E. Wulff 《Chemical science》2021,12(11):4147
Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer. 相似文献
14.
Lucia D'Accolti Cosimo Annese Antonella Aresta Caterina Fusco 《Journal of heterocyclic chemistry》2014,51(5):1482-1486
Epoxides are essential building blocks in organic chemistry. The epoxidation of unsubstituted cyclic dienes 2 , 3 , 4 and triene 5 using dimethyldioxirane ( 1a ) and its trifluoro analog 1b methyl(trifluoromethyl)dioxirane has been investigated. The excellent yields obtained (90–98%) are accompanied by outstandingly high diastereoselectivities (90–98%). Interpretation of results based upon the early idea that polar groups can direct the dioxirane attack by dipole–dipole interaction provides a likely rationale, along with a more generalized mechanistic view. 相似文献
15.
Caterina Viglianisi Stefano Menichetti Giulio Assanelli Maria Carmela Sacchi Incoronata Tritto Simona Losio 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4647-4655
A new family of ethylene‐based copolymers with controlled amounts of a norbornene comonomer (NArOH) bearing a stabilizing antioxidant functionality (2,6‐di‐tert‐butyl phenol) was prepared. Due to unavoidable exo/endo equilibrium operative in NArOH comonomer, a complete and detailed NMR assignment of the structure of the prepared ethylene/NArOH copolymers was carried out for the determination of the exo/endo ratio inside the polymer. These novel functionalized comonomers can be considered suitable starting material for preparing ethylene‐based copolymers, with tunable comonomer content, as non‐releasing macromolecular antioxidant additives for specific application in safe food and/or drug packaging © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
16.
Giuseppe Leone Antonella Caterina Boccia Giovanni Ricci Antonino Giarrusso Lido Porri 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3227-3232
(E)‐1,3‐Pentadiene (EP) and (E)‐2‐methyl‐1,3‐pentadiene (2MP) were polymerized to cis‐1,4 polymers with homogeneous and heterogeneous neodymium catalysts to examine the influence of the physical state of the catalyst on the polymerization stereoselectivity. Data on the polymerization of (E)‐1,3‐hexadiene (EH) are also reported. EP and EH gave cis‐1,4 isotactic polymers both with the homogeneous and with the heterogeneous system, whereas 2MP gave an isotactic cis‐1,4 polymer with the heterogeneous catalyst and a syndiotactic cis‐1,4 polymer, never reported earlier, with the homogeneous one. For comparison, the results obtained with the soluble CpTiCl3‐based catalyst (Cp = cyclopentadienyl), which gives cis‐1,4 isotactic poly(2MP), are examined. A tentative interpretation is given for the mechanism of the formation of the stereoregular polymers obtained and a complete NMR characterization of the cis‐1,4‐syndiotactic poly(2MP) is reported. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3227–3232 相似文献
17.
18.
Caterina Calgaro Claire Colin Emmanuel Creus Ezzeddine Zahrouni 《Mathematical Methods in the Applied Sciences》2019,42(1):250-271
In this work, we prove the existence and the uniqueness of the strong solution of a low‐Mach model, for which the dynamic viscosity of the fluid is a given function of its temperature. The method is based on the convergence study of a sequence towards the solution, for which the rates are also given. The originality of the approach is to consider the system in terms of the temperature and the velocity, leading to a nonlinear temperature equation and the development of some specific tools and results. 相似文献
19.
Caterina Costa Carmela Cavalcante Francesca Zito Yukio Yokota Valeria Matranga 《Molecular diversity》2010,14(4):653-665
The extracellular matrix protein Pl-nectin, a 210-kDa homodimer originally purified from sea urchin eggs, plays a crucial role in cell adhesion and embryonic
morphogenesis. The compiled cDNA sequence, obtained by RT-PCR primer walking and 3′ RACE, identified a 984aa product containing
a 23aa signal peptide and including all six internal peptides identified by protein microsequencing. The protein is a new
member of the galactose-binding protein superfamily as it consists of six 151–156aa-long tandemly repeated domains (D1–D6),
homologous to the discoidin-like domains, also known as F5/8-type C domains. Based on homology modelling, we present a three-dimensional
structure (3D) for D5, identified as the prototype domain. The molecular modelling of the assembled Pl-nectin homodimer accounts for a Pl-nectin quaternary structure composed of two 105-kDa C-shaped monomers linked by a S–S bridge. The presence of an LDT motif
between the first and the second exposed loops of the D2 domain suggests the binding of Pl-nectin to an integrin receptor. Altogether, the in silico analysis described here is consistent with previous biochemical
reports and offers a basis for predictions to be experimentally tested. 相似文献
20.
Caterina Fraschetti Antonello Filippi Maria Elisa Crestoni Tadashi Ema Maurizio Speranza 《Journal of the American Society for Mass Spectrometry》2013,24(4):573-578
The most common protocols for the quantitative determination of the enantiomeric excess (ee) of raw mixtures by ESI-MS reveal inadequate in cases where the distribution of diastereomeric derivatives diverges from the ee of original solutions. This phenomenon is attributable to a matrix effect, i.e., to the stereospecific formation of high order noncovalent adducts in the ESI droplets, which alters the actual availability of the diastereomeric species under MS analysis. In this frame, the assumption of classic protocols that the ionization correction factor q is independent on the composition of the mixture submitted to analysis is questionable. An alternative methodology is presented in this paper, which is aimed at circumventing the problem by excluding any chemical derivatization of the original raw mixture. It is based on the measurement of the actual distribution of ESI-formed proton-bound diastereomeric complexes from the enantiomeric mixture through a careful analysis of their reaction kinetics with a suitable reactant. 相似文献