全文获取类型
收费全文 | 1260篇 |
免费 | 56篇 |
国内免费 | 2篇 |
专业分类
化学 | 1103篇 |
晶体学 | 7篇 |
力学 | 13篇 |
数学 | 68篇 |
物理学 | 127篇 |
出版年
2023年 | 13篇 |
2022年 | 110篇 |
2021年 | 98篇 |
2020年 | 33篇 |
2019年 | 26篇 |
2018年 | 26篇 |
2017年 | 35篇 |
2016年 | 67篇 |
2015年 | 53篇 |
2014年 | 74篇 |
2013年 | 99篇 |
2012年 | 113篇 |
2011年 | 96篇 |
2010年 | 62篇 |
2009年 | 50篇 |
2008年 | 64篇 |
2007年 | 63篇 |
2006年 | 46篇 |
2005年 | 51篇 |
2004年 | 33篇 |
2003年 | 28篇 |
2002年 | 17篇 |
2001年 | 9篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1928年 | 1篇 |
排序方式: 共有1318条查询结果,搜索用时 15 毫秒
21.
Miguel F. Braa Jos M. Castellano Maria L. Lpez Rodriguez Magdalena Glvez Manuel R. Amil Enrique Rubio 《Journal of heterocyclic chemistry》1987,24(2):369-371
Hydrolysis of N,N'-diacyl-1,2-di(4-pyridyl)ethylenediamines 1 in aqueous sulfuric acid gave the corresponding imidazolines 3. 1,2-Di-(4-pyridyl)ethylenediamine 2 was prepared in 61 % yield by treating N,N'-di-t-butyl-oxycarbonyl-1,2-di(4-pyridyl)ethylenediamine 4 with trifluoroacetic acid or in 94% yield by the hydrolysis under basic conditions of N,N'-diphthaloylglycyl-1,2-di(4-pyridy)ethylenediamine 13. 相似文献
22.
Reaction of 3-methoxycarbonyl-2-methyl- or 3-dimethoxyphosphoryl-2-methyl-substituted 4-oxo-4H-chromones 1 with N-methylhydrazine resulted in the formation of isomeric, highly substituted pyrazoles 4 (major products) and 5 (minor products). Intramolecular transesterification of 4 and 5 under basic conditions led, respectively, to tricyclic derivatives 7 and 8. The structures of pyrazoles 4a (dimethyl 2-methyl-4-oxo-4H-chromen-3-yl-phosphonate) and 4b (methyl 4-oxo-2-methyl-4H-chromene-3-carboxylate) were confirmed by X-ray crystallography. Pyrazoles 4a and 4b were used as ligands (L) in the formation of ML2Cl2 complexes with platinum(II) or palladium(II) metal ions (M). Potassium tetrachloroplatinate(II), used as the metal ion reagent, gave both trans-[Pt(4a)2Cl2] and cis-[Pt(4a)2Cl2], complexes with ligand 4a, and only cis-[Pt(4b)2Cl2] isomer with ligand 4b. Palladium complexes were obtained by the reaction of bis(benzonitrile)dichloropalladium(II) with the test ligands. trans-[Pd(4a)2Cl2] and trans-[Pd(4b)2Cl2] were the exclusive products of these reactions. The structures of all the complexes were confirmed by IR, 1H NMR and FAB MS spectral analysis, elemental analysis and Kurnakov tests. 相似文献
23.
Roman Major Grayna Wilczek Justyna Wicek Maciej Gawlikowski Hanna Plutecka Katarzyna Kasperkiewicz Marcin Kot Magorzata Pomorska Roman Ostrowski Magdalena Kopernik 《Molecules (Basel, Switzerland)》2022,27(17)
The aim of this study was to minimize the risk of life-threatening thromboembolism in the ventricle through the use of a new biomimetic heart valve based on metal–polymer composites. Finite volume element simulations of blood adhesion to the material were carried out, encompassing radial flow and the cone and plane test together with determination of the effect of boundary conditions. Both tilt-disc and bicuspid valves do not have optimized blood flow due to their design based on rigid valve materials (leaflet made of pyrolytic carbon). The main objective was the development of materials with specific properties dedicated to contact with blood. Materials were evaluated by dynamic tests using blood, concentrates, and whole human blood. Hemostability tests under hydrodynamic conditions were related to the mechanical properties of thin-film materials obtained from tribological tests. The quality of the coatings was high enough to avoid damage to the coating even as they were exposed up to maximum loading. Analysis towards blood concentrates of the hydrogenated carbon sample and the nitrogen-doped hydrogenated carbon sample revealed that the interaction of the coating with erythrocytes was the strongest. Hemocompatibility evaluation under hydrodynamic conditions confirmed very good properties of the developed coatings. 相似文献
24.
Rosa Sparaco Ewa Kdzierska Agnieszka A. Kaczor Anna Bielenica Elisa Magli Beatrice Severino Angela Corvino Ewa Gibua-Tarowska Jolanta H. Kotliska Giorgia Andreozzi Paolo Luciano Elisa Perissutti Francesco Frecentese Marcello Casertano Anna Leniak Magdalena Bujalska-Zadrony Magorzata Ozibo Raffaele Capasso Vincenzo Santagada Giuseppe Caliendo Ferdinando Fiorino 《Molecules (Basel, Switzerland)》2022,27(19)
A new series of 5-norbornene-2-carboxamide derivatives was prepared and their affinities to the 5-HT1A, 5-HT2A, and 5-HT2C receptors were evaluated and compared to a previously synthesized series of derivatives characterized by exo-N-hydroxy-5-norbornene-2,3-dicarboximidenucleus, in order to identify selective ligands for the above-mentioned subtype receptors. Arylpiperazines represents one of the most important classes of 5-HT1AR ligands, and recent research concerning new derivatives has been focused on the modification of one or more portions of such pharmacophore. The combination of structural elements (heterocyclic nucleus, propyl chain and 4-substituted piperazine), known to be critical to the affinity to 5-HT1A receptors, and the proper selection of substituents led to compounds with high specificity and affinity towards serotoninergic receptors. The most active compounds were selected for further in vivo assays to determine their functional activity. Finally, to rationalize the obtained results, molecular docking studies were performed. The results of the pharmacological studies showed that Norbo-4 and Norbo-18 were the most active and promising derivatives for the serotonin receptor considered in this study. 相似文献
25.
Monika Jamio Magdalena Sozoniuk Jacek Wawrzykowski Marta Kankofer 《Molecules (Basel, Switzerland)》2022,27(21)
Changes in the expression of various genes, including pregnancy-associated hormone receptors and extracellular matrix proteins, have been suggested to play a significant role in bovine placental development. This study aimed to examine the influence of sex steroids and PGF2α on decorin (DCN) expression in the epithelial cells of bovine caruncle in early–mid pregnancy in cows. The expression patterns of DCN, PTGFR, PGR and ESR1 were analyzed by RT-qPCR and Western blotting in primary caruncular epithelial cell cultures (PCECC) and placental tissue homogenates derived from the 2nd and 4th months of pregnancy. PCECC were found to express DCN, PTGFR, PGR and ESR1. The intensity of PGR staining was higher in cells derived from the 4th month of pregnancy (p < 0.05). The 17β-estradiol, progesterone and PGF2α have not been shown to affect DCN expression. PGF2α decreased PTGFR expression in cells derived from the 4th month of gestation (p < 0.05). In conclusion, the results of the present preliminary study showed that the expression of the PTGFR, ESR1, PGR and DCN in PCECC does not vary throughout early–mid pregnancy. Further studies should be carried out to observe the relationship between hormonal status and cellular adhesion to determine their importance for properly developing placentation and pregnancy in cows. 相似文献
26.
Wioleta Ciempiel Magdalena Czemierska Monika Szymaska-Chargot Artur Zdunek Dariusz Wicek Anna Jarosz-Wilkoazka Izabela Krzemiska 《Molecules (Basel, Switzerland)》2022,27(21)
In the present study, the potential of lead and cadmium removal by the extracellular polymeric substances (EPS) produced from Parachlorella kessleri and Chlorella vulgaris were investigated. Carbohydrates were the dominant components of EPS from both analyzed species. The contents of reducing sugars, uronic acids, and amino acids were higher in EPS synthesized by C. vulgaris than in EPS from P. kessleri. The analysis of the monosaccharide composition showed the presence of rhamnose, mannose and galactose in the EPS obtained from both species. The ICP-OES (inductively coupled plasma optical emission spectrometry) analyses demonstrated that C. vulgaris EPS showed higher sorption capacity in comparison to P. kessleri EPS. The sorption capacity of C. vulgaris EPS increased with the increase in the amount of metal ions. P. kessleri EPS had a maximum sorption capacity in the presence of 100 mg/L of metal ions. The FTIR analysis demonstrated that the carboxyl, hydroxyl, and carbonyl groups of EPS play a key role in the interactions with metal ions. The present study showed C. vulgaris EPS can be used as a biosorbent in bioremediation processes due to its biochemical composition, the presence of significant amounts of negatively charged uronic acids, and higher sorption capacity. 相似文献
27.
Sergio O. Serna-Hernandez Zamantha Escobedo-Avellaneda Rebeca García-García Magdalena de Jesús Rostro-Alanis Jorge Welti-Chanes 《Molecules (Basel, Switzerland)》2022,27(21)
The effect of different high-pressure processing (HPP) treatments on casein micelles was analyzed through scanning electron microscopy (SEM) and a particle size distribution analysis. Raw whole and skim milk samples were subjected to HPP treatments at 400, 500 and 600 MPa for Come-Up Times (CUT) up to 15 min at ambient temperature. Three different phenomena were observed in the casein micelles: fragmentation, alterations to shape and agglomeration. The particle size distribution analysis determined that, as pressure and time treatment increased, the three phenomena intensified. First, the size of the casein micelles began to decrease as their fragmentation occurred. Subsequently, the casein micelles lost roundness, and their shape deformed. Finally, in the most intense treatments (higher pressures and/or longer times), the micelles fragments began to agglomerate, which resulted in an increase in their average diameter. Homogenization and defatting had no significant effect on the casein micelles; however, the presence of fat in whole milk samples was bioprotective, as the effects of the three phenomena appeared faster in treated skim milk samples. Through this study, it was concluded that the size and structure of casein micelles are greatly altered during high-pressure treatment. These results provide information that broadens the understanding of the changes induced on casein micelles by high-pressure treatments at room temperature. 相似文献
28.
Joanna Kubik ukasz Waszak Grzegorz Adamczuk Ewelina Humeniuk Magdalena Iwan Kamila Adamczuk Mariola Michalczuk Agnieszka Korga-Plewko Aleksandra Jzefczyk 《Molecules (Basel, Switzerland)》2022,27(21)
The Centaurea L. (Asteraceae) genus includes many plant species with therapeutic properties. Centaurea castriferrei Borbás & Waisb is one of the least known and least described plants of this genus. The aim of the study was the phytochemical analysis of water and methanol–water extracts (7:3 v/v) obtained from the aerial parts of the plant as well as evaluation of their anticancer activity. Quantitative determinations of phenolic compounds and flavonoids were performed, and the antioxidant potential was measured using the CUPRAC method. The RP-HPLC/DAD analysis and HPLC-ESI-QTOF-MS mass spectroscopy were performed, to determine the extracts’ composition. The antiproliferative activity of the obtained extracts was tested in thirteen cancer cell lines and normal skin fibroblasts using MTT test. Regardless of the extraction method and the extractant used, similar cytotoxicity of the extracts on most cancer cell lines was observed. However, the methanol–water extracts (7:3 v/v) contained significantly more phenolic compounds and flavonoids as well as showing stronger antioxidant properties in comparison to water extracts. Centaurea castriferrei Borbás & Waisb is a rich source of apigenin and its derivatives. In all tested extracts, chlorogenic acid and centaurein were also identified. In vitro research revealed that this plant may be a potential source of compounds with anticancer activity. 相似文献
29.
Magdalena Barwiolek Dominika Jankowska Anna Kaczmarek-Kdziera Slawomir Wojtulewski Lukasz Skowroski Tomasz Rerek Pawe Popielarski Tadeusz M. Muziol 《Molecules (Basel, Switzerland)》2022,27(21)
Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes. 相似文献
30.
Katarzyna Szymczyk Andrzej Lewandowski Anna Zdziennicka Magdalena Szaniawska Bronisaw Jaczuk 《Molecules (Basel, Switzerland)》2022,27(23)
The studies on the behavior of Auramine O (AuO) at the water–air interface and in the bulk phase of the aqueous solution of Kolliphor® ELP (ELP) and Kolliphor® RH 40 (RH40) and their mixture were based on the results obtained from the measurements of the contact angle of water, formamide and diiodomethane on the polytetrafluoroethylene covered by the AuO layer, the surface tension of the aqueous solution of AuO, AuO + ELP, AuO + RH40, AuO + ELP + RH40, density and fluorescence intensity. Based on the obtained results, it was possible to determine components and parameters of the AuO surface tension, concentration and composition of the mixed monolayer, including AuO, ELP and RH40, as well as that of the mixed micelles, and to determine the Gibbs standard free energy of adsorption, micellization and AuO solubilization. The obtained results also showed that surface tension isotherms of the studied solutions can be described by the Szyszkowski equation and the exponential function of the second order and predicted by the Fainerman and Miller equation. In addition, the mixed surface layer composition can be predicted based on the contribution of the components of this layer to the water surface tension reduction. 相似文献