全文获取类型
收费全文 | 154篇 |
免费 | 1篇 |
专业分类
化学 | 111篇 |
晶体学 | 1篇 |
数学 | 10篇 |
物理学 | 33篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 2篇 |
2019年 | 1篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 2篇 |
2014年 | 5篇 |
2013年 | 5篇 |
2012年 | 9篇 |
2011年 | 4篇 |
2010年 | 8篇 |
2009年 | 7篇 |
2008年 | 9篇 |
2007年 | 11篇 |
2006年 | 8篇 |
2005年 | 2篇 |
2004年 | 8篇 |
2003年 | 2篇 |
2002年 | 8篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有155条查询结果,搜索用时 62 毫秒
61.
Abstract The susceptibility of the fully acetylated 1-thio–β-D-glucopyranosyl esters of N-protected amino acids toward the amino group of an external amino acid-or peptide-ester was examined in dichloromethane at room temperature and at 40°, respectively. In each case, the aminolysis reaction led to rupture of the C-1 thiolester bond and formation of the corresponding N-acylpeptide ester; the reaction proceeded without racemization of the aglycon chiral centre. Evidence for a remarkably high acylating efficiency of the sugar—amino acid C-1 thiolester bond is presented. 相似文献
62.
The corrosion resistance of AISI 420 stainless steel in 0.1 mol L?1 H2SO4 + 0.1 mol L?1 Na2SO4 solutions at different pH-values and the inhibiting effect of Ce3+ ions was studied using electrochemical polarization methods. The results reveal decreasing of the corrosion rate with an increasing the pH of the solution, which demonstrates the progressive protective character of the inhibitor used. At pH lower than 3.33, the corrosion inhibition was most probably a result of the competitive adsorption of Ce3+ with H+ ions on the cathodic sites of the electrode surface, and it was found to be dependent on the relative concentration of H+/Ce3+. The peroxide generated from the oxygen reduction reaction at pH 3.33 was found to be capable oxidize trivalent cerium (Ce) to the tetravalent state. As obtained hydroxide precipitates act as diffusion barrier hindering the corrosion processes, whereafter a spontaneous passivity occurs on the steel surface at this pH. 相似文献
63.
Experiments to determine the mercury methylation potential were performed on sediments from two locations on the river Idrijca
(Slovenia), differing in ambient mercury concentrations. The tracer used was the radioactive isotope 197Hg. The benefit of using this tracer is its high specific activity, which enables spikes as low as 0.02 ng Hg2+ g−1 of sample to be used. It was therefore possible to compare the efficiency of the methylation potential experiments over a
range of spike concentrations from picogram to microgram levels. The first part of the work aimed to validate the experimental
blanks and the second part consisted of several series of incubation experiments on two different river sediments using a
range of tracer additions. The results showed high variability in the obtained methylation potentials. Increasing Hg2+ additions gave a decrease in the percentage of the tracer methylated during incubation; in absolute terms, the spikes that
spanned four orders of magnitude (0.019–190 pg g−1 of sediment slurry) resulted in MeHg formation between 0.01 and 0.1 ng MeHg g−1 in Podroteja and Kozarska Grapa. Higher spikes resulted in slightly elevated MeHg production (up to a maximum of 0.27 ng g−1). The values of methylation potential were similar in both sediments. The results imply that the experimental determination
of mercury methylation potential strongly depends on the experimental setup itself and the amount of tracer added to the system
under study. It is therefore recommended to use different concentrations of tracer and perform the experiments in several
replicates. The amount of mercury available for methylation in nature is usually very small. Therefore, adding very low amounts
of tracer in the methylation potential studies probably gives results that have a higher environmental relevance. It is also
suggested to express the results obtained in absolute amounts of MeHg produced and not just as the percentage of the added
tracer. 相似文献
64.
Basarić N Horvat M Mlinarić-Majerski K Zimmermann E Neudörfl J Griesbeck AG 《Organic letters》2008,10(18):3965-3968
The photochemical reaction of N-(1-adamantyl)phthalimide (1) gives cleanly one product, the novel hexacyclic benzazepine derivative of 2,4-methanoadamantane 2. Its structure was characterized by spectroscopic methods and X-ray analysis and represent the first example of the 2-azahexacyclo[8.7.1.1 (1,4).0 (4,9).0 (11,16).0 (12,18)]nonadeca-4,6,8-triene skeleton. The product is formed by a domino process of two consecutive excited-state intramolecular gamma-hydrogen-transfer reactions. Base hydrolysis of the benzazepine 2 gives in high yield the keto derivative of the 1,2-substituted adamantane epsilon-amino acid 3. 相似文献
65.
Uroš Grošelj Amalija Golobič Damijan Knez Martina Hrast Stanislav Gobec Sebastijan Ričko Jurij Svete 《Molecular diversity》2016,20(3):667-676
The synthesis of two novel (+)-isocampholenic acid-derived amines has been realized starting from commercially available (1S)-(+)-10-camphorsulfonic acid. The novel amines as well as (+)-isocampholenic acid have been used as building blocks in the construction of a library of amides using various aliphatic, aromatic, and amino acid-derived coupling partners using BPC and CDI as activating agents. Amide derivatives have been assayed against several enzymes that hold potential for the development of new drugs to battle bacterial infections and Alzheimer’s disease. Compounds 20c and 20e showed promising selective sub-micromolar inhibition of human butyrylcholinesterase \((h\hbox {BChE})\) (\(\hbox {IC}_{50}\) values \(0.80\,\pm 0.05\) and \(0.25\,\pm 0.02\,{\upmu }\hbox {M}\), respectively). 相似文献
66.
Makarević J Štefanić Z Horvat L Žinić M 《Chemical communications (Cambridge, England)》2012,48(59):7407-7409
Chiral amino acid and biphenyl incorporating oxalamide gelators 4-7 with large, 9 bond distance between chiral centres and biphenyl units have been studied. CD investigation of 4-octanol gel and the crystal structure of rac-4 reveal that efficient central to axial chirality transfer occurs by intermolecular interactions in gel and solid state assemblies. 相似文献
67.
The generalized vehicle routing problem (GVRP) is an extension of the vehicle routing problem (VRP) and was introduced by Ghiani and Improta [1]. The GVRP is the problem of designing optimal delivery or collection routes from a given depot to a number of predefined, mutually exclusive and exhaustive node-sets (clusters) which includes exactly one node from each cluster, subject to capacity restrictions. The aim of this paper is to provide two new models of the GVRP based on integer programming. The first model, called the node formulation is similar to the Kara-Bekta? formulation [2], but produces a stronger lower bound. The second one, called the flow formulation, is completely new. We show as well that under specific circumstances the proposed models of the GVRP reduces to the well known routing problems. Finally, the GVRP is extended for the case in which the vertices of any cluster of each tour are contiguous. This case is defined as the clustered generalized vehicle routing problem and both of the proposed formulations of GVRP are adapted to clustered case. 相似文献
68.
We study the existence and properties of wormhole throats in modified f (R) gravity theory. Specifically, we concentrate on the cases where the lapse is not necessarily constant, and hence are not limited to the zero tidal force scenarios. In the class of theories whose actions are generated by Lagrangians of the form f (R)?=?∑ α n ?R n we find parameters which allow for the existence of energy condition respecting throats, which do not exist in Einstein gravity. We also consider the effect of the modified action on the anisotropy of the models, and find that modified gravity can minimize the amount of anisotropy required to support the existence of a throat. In both these respects, the sector containing theories with positive n is more promising than the negative n sector in comparison to Einstein gravity alone, with large n being most favorable. 相似文献
69.
An effective quantum field theory (QFT) with a manifest UV/IR connection, so as to be valid for arbitrarily large volumes, can successfully be applied to the cosmological dark energy problem as well as the cosmological constant (CC) problem. Motivated by recent approaches to the hierarchy problem, we develop such a framework with a large number of particle species. When applying to systems on the brink of experiencing a sudden collapse to a black hole, we find that the entropy, unlike the total energy, now becomes an increasing function of the number of field species. An internal consistency of the theory is then used to infer the upper bound on the number of particle species, showing consistency with the holographic Bekenstein–Hawking bound. This may thus serve to fill in a large gap in entropy of any non-black hole configuration of matter and the black holes. In addition, when the bound is saturated the entanglement entropy matches the black hole entropy, thus solving the multiplicity of species problem. In a cosmological setting, the maximum allowable number of species becomes a function of cosmological time, reaching its minimal value in a low-entropy post-reheating epoch. 相似文献
70.
Ivan Petters Matija Modruan Nikolina Vidovi Ivo Crnolatac Nikola Cindro Ivo Piantanida Giovanna Speranza Gordan Horvat Vladislav Tomii 《Molecules (Basel, Switzerland)》2022,27(12)
Cyclic pentaphenylalanine was studied as an efficient anion sensor for halides, thiocyanate and oxoanions in acetonitrile and methanol. Stability constants of the corresponding complexes were determined by means of fluorimetric, spectrophotometric, 1H NMR, and microcalorimetric titrations. A detailed structural overview of receptor–anion complexes was obtained by classical molecular dynamics (MD) simulations. The results of 1H NMR and MD studies indicated that the bound anions were coordinated by the amide groups of cyclopeptide, as expected. Circular dichroism (CD) titrations were also carried out in acetonitrile. To the best of our knowledge, this is the first example of the detection of anion binding by cyclopeptide using CD spectroscopy. The CD spectra were calculated from the structures obtained by MD simulations and were qualitatively in agreement with the experimental data. The stoichiometry of almost all complexes was 1:1 (receptor:anion), except for dihydrogen phosphate where the binding of dihydrogen phosphate dimer was observed in acetonitrile. The affinity of the cyclopeptide receptor was correlated with the structure of anion coordination sphere, as well as with the solvation properties of the examined solvents. 相似文献