全文获取类型
收费全文 | 1287篇 |
免费 | 28篇 |
国内免费 | 2篇 |
专业分类
化学 | 1063篇 |
晶体学 | 22篇 |
力学 | 4篇 |
数学 | 108篇 |
物理学 | 120篇 |
出版年
2023年 | 14篇 |
2022年 | 77篇 |
2021年 | 55篇 |
2020年 | 31篇 |
2019年 | 33篇 |
2018年 | 22篇 |
2017年 | 23篇 |
2016年 | 48篇 |
2015年 | 41篇 |
2014年 | 45篇 |
2013年 | 116篇 |
2012年 | 86篇 |
2011年 | 77篇 |
2010年 | 51篇 |
2009年 | 59篇 |
2008年 | 54篇 |
2007年 | 65篇 |
2006年 | 62篇 |
2005年 | 47篇 |
2004年 | 51篇 |
2003年 | 36篇 |
2002年 | 26篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 16篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1962年 | 2篇 |
排序方式: 共有1317条查询结果,搜索用时 15 毫秒
101.
Ewa Wagner-Wysiecka Natalia ukasik Andrzej Okuniewski Baej Galiski 《Monatshefte für Chemie / Chemical Monthly》2020,151(3):331-343
The synthesis and ion binding properties of new amide derived from propeller-like tris(2-pyridyl)amine and 2,6-pyridinedicarboxylic acid chloride were described. Amide binds divalent metal cations: copper(II), nickel(II), zinc(II), and lead(II) in acetonitrile. In acetonitrile:water mixture (9:1 v/v) amide interacts only with copper(II) and nickel(II) cations forming complexes of 1:1 stoichiometry. It was found that the introduction of bulky, nitrogen donor atom bearing pendant groups can influence coordination mode of pyridine-2,6-dicarboxamides. The probable model of ligand-ion interactions is proposed on the basis of 1H NMR and FT-IR spectroscopy. 相似文献
102.
Manuel G. Ricardo Ameena M. Ali Jacek Plewka Ewa Surmiak Beata Labuzek Constantinos G. Neochoritis Jack Atmaj Lukasz Skalniak Ran Zhang Tad A. Holak Matthew Groves Daniel G. Rivera Alexander Dmling 《Angewandte Chemie (International ed. in English)》2020,59(13):5235-5241
Stapled peptides are chemical entities in‐between biologics and small molecules, which have proven to be the solution to high affinity protein–protein interaction antagonism, while keeping control over pharmacological performance such as stability and membrane penetration. We demonstrate that the multicomponent reaction‐based stapling is an effective strategy for the development of α‐helical peptides with highly potent dual antagonistic action of MDM2 and MDMX binding p53. Such a potent inhibitory activity of p53‐MDM2/X interactions was assessed by fluorescence polarization, microscale thermophoresis, and 2D NMR, while several cocrystal structures with MDM2 were obtained. This MCR stapling protocol proved efficient and versatile in terms of diversity generation at the staple, as evidenced by the incorporation of both exo‐ and endo‐cyclic hydrophobic moieties at the side chain cross‐linkers. The interaction of the Ugi‐staple fragments with the target protein was demonstrated by crystallography. 相似文献
103.
Ewa esawska Izabela Korona-Gowniak Wojciech Nitek Waldemar Tejchman 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):359-366
Derivatives of pyrimidine‐2(1H)‐selenone are a group of compounds with very strong antimicrobial activity. In order to study the effect of the position of the methoxy substituent on biological activity, molecular geometry and intermolecular interactions in the crystal, three derivatives were prepared and evaluated with respect to their antimicrobial activities, and their crystal structures were determined by X‐ray diffraction. The investigated compounds, namely, 1‐(X‐methoxyphenyl)‐4‐methyl‐6‐phenylpyrimidine‐2(1H)‐selenones (X = 2, 3 and 4 for 1 , 2 and 3 , respectively), C18H16N2OSe, showed very strong activity against selected strains of Gram‐positive bacteria and fungi. Two compounds, 1 and 2 , crystallize in the monoclinic space group P21/c, while 3 crystallizes in the space group P21/n; 1 has two molecules in the asymmetric unit and the other two ( 2 and 3 ) have one molecule. The geometries of the investigated compounds differ slightly in the mutual orientations of the aromatic and pyrimidineselenone rings. The O atom in 1 stabilizes the conformation of the molecules via intramolecular C—H…O hydrogen bonding. The packing of molecules is determined by weak C—H…N and C—H…Se intermolecular interactions and additionally in 1 and 2 by C—H…O intermolecular interactions. The introduction of the methoxy substituent results in greater selectivity of the investigated compounds. 相似文献
104.
105.
Ewa Wagner-Wysiecka Paulina Szulc Elbieta Luboch Jarosaw Chojnacki Pawe Sowiski Katarzyna Szwarc-Karabyka 《Molecules (Basel, Switzerland)》2022,27(6)
The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement—t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH—were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo–phenol⇄quinone–hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. 1H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH. 相似文献
106.
Joanna Klebeko Paula Ossowicz-Rupniewska Ewelina
witek Joanna Szachnowska Ewa Janus Stefka G. Taneva Elena Krachmarova Maya Guncheva 《Molecules (Basel, Switzerland)》2022,27(1)
In recent years, numerous studies have shown that conversion of conventional drugs in ionic liquid (IL) formulation could be a successful strategy to improve their physicochemical properties or suggest a new route of administration. We report the synthesis and detailed characterization of eight salicylic acid-based ILs (SA-ILs) containing cation non-polar or aromatic amino acid esters. Using in vitro assays, we preliminary evaluated the therapeutic potency of the novel SA-ILs. We observed that conversion of the SA into ionic liquids led to a decrease in its cytotoxicity toward NIH/3T3 murine embryo fibroblasts and human HaCaT keratinocytes. It should be mentioned is that all amino acid alkyl ester salicylates [AAOR][SA] inhibit the production of the proinflammatory cytokine IL-6 in LPS-stimulated keratinocytes. Moreover, keratinocytes, pretreated with [PheOMe][SA] and [PheOPr][SA] seem to be protected from LPS-induced inflammation. Finally, the novel compounds exhibit a similar binding affinity to bovine serum albumin (BSA) as the parent SA, suggesting a similar pharmacokinetic profile. These preliminary results indicate that SA-ILs, especially those with [PheOMe], [PheOPr], and [ValOiPr] cation, have the potential to be further investigated as novel topical agents for chronic skin diseases such as psoriasis and acne vulgaris. 相似文献
107.
Gniewomir Latacz Kinga Saat Anna Furgaa-Wojas Adrian Martyniak Agnieszka Olejarz-Maciej Ewelina Honkisz-Orzechowska Ewa Szymaska 《Molecules (Basel, Switzerland)》2022,27(3)
Trying to meet the multitarget-directed ligands strategy, a series of previously described aryl-substituted phenylalanine derivatives, reported as competitive antagonists of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptors, were screened in vitro for their free-radical scavenging and antioxidant capacity in two different assays: ferric reducing antioxidant power (FRAP) and oxygen radical absorbance capacity fluorescent (ORAC-FL) assays. The most active antioxidants 1 and 8 were further examined to evaluate their neuroprotective properties in vitro. In this study, compound 1 showed a significant neuroprotective effect against the neurotoxin 6-hydroxydopamine in neuroblastoma SH-SY5Y and IMR-32 cell lines. Both compounds also showed prevention from high levels of reactive oxygen species (ROS) in SH-SY5Y cells. Furthermore, the desired monoamine oxidase B (MAO-B) inhibition effect (IC50 = 278 ± 29 nM) for 1 was determined. No toxic effects up to 100 µM of 1 and 8 against neuroblastoma cells were observed. Furthermore, in vivo studies showed that compound 1 demonstrated significant anticonvulsant potential in 6-Hz test, but in neuropathic pain models its antiallodynic and antihyperalgesic properties were not observed. Concluding, the compound 1 seems to be of higher importance as a new phenylalanine-based lead candidate due to its confirmed promise in in vitro and in vivo anticonvulsant activity. 相似文献
108.
Angelika Macior Izabela Zaborniak Pawe Chmielarz Joanna Smenda Karol Wolski Ewa Ciszkowicz Katarzyna Lecka-Szlachta 《Molecules (Basel, Switzerland)》2022,27(3)
The article presents the modification of ash wood via surface initiated activators regenerated by electron transfer atom transfer radical polymerization mediated by elemental silver (Ag0 SI-ARGET ATRP) at a diminished catalyst concentration. Ash wood is functionalized with poly(methyl methacrylate) (PMMA) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) to yield wood grafted with PMMA-b-PDMAEMA-Br copolymers with hydrophobic and antibacterial properties. Fourier transform infrared (FT-IR) spectroscopy confirmed the covalent incorporation of functional ATRP initiation sites and polymer chains into the wood structure. The polymerization kinetics was followed by the analysis of the polymer grown in solution from the sacrificial initiator by proton nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). The polymer layer covalently attached to the wood surface was observed by scanning electron microscopy (SEM). The hydrophobic properties of hybrid materials were confirmed by water contact angle measurements. Water and sodium chloride salt aqueous solution uptake tests confirmed a significant improvement in resistance to the absorption of wood samples after modification with polymers. Antibacterial tests revealed that wood-QPDMAEMA-Br, as well as wood-PMMA-b-QPDMAEMA-Br, exhibited higher antibacterial activity against Gram-positive bacteria (Staphylococcus aureus) in comparison with Gram-negative bacteria (Escherichia coli). The paper presents an economic concept with ecological aspects of improving wood properties, which gives great opportunities to use the proposed approach in the production of functional hybrid materials for industry and high quality sports equipment, and in furniture production. 相似文献
109.
A sufficient condition of viability for fractional differential equations with the Caputo derivative
Ewa Girejko Ma?gorzata Wyrwas 《Journal of Mathematical Analysis and Applications》2011,381(1):146-231
In this paper viability results for nonlinear fractional differential equations with the Caputo derivative are proved. We give the sufficient condition that guarantees fractional viability of a locally closed set with respect to nonlinear function. As an example we discuss positivity of solutions, particularly in linear case. 相似文献
110.
Ewa M. Bednarczuk Enrico Miglierina Elena Molho 《Set-Valued and Variational Analysis》2011,19(4):569-587
The mountain pass theorem for scalar functionals is a fundamental result of the minimax methods in variational analysis. In this work we extend this theorem to the class of \(\mathcal{C}^{1}\) functions \(f:\mathbb{R}^{n}\rightarrow\mathbb{R}^{m}\), where the image space is ordered by the nonnegative orthant \(\mathbb{R}_{+}^{m}\). Under suitable geometrical assumptions, we prove the existence of a critical point of f and we localize this point as a solution of a minimax problem. We remark that the considered minimax problem consists of an inner vector maximization problem and of an outer set-valued minimization problem. To deal with the outer set-valued problem we use an ordering relation among subsets of \(\mathbb{R}^{m}\) introduced by Kuroiwa. In order to prove our result, we develop an Ekeland-type principle for set-valued maps and we extensively use the notion of vector pseudogradient. 相似文献