全文获取类型
收费全文 | 2033篇 |
免费 | 58篇 |
国内免费 | 3篇 |
专业分类
化学 | 1642篇 |
晶体学 | 13篇 |
力学 | 26篇 |
数学 | 228篇 |
物理学 | 185篇 |
出版年
2024年 | 3篇 |
2023年 | 13篇 |
2022年 | 70篇 |
2021年 | 93篇 |
2020年 | 61篇 |
2019年 | 48篇 |
2018年 | 36篇 |
2017年 | 29篇 |
2016年 | 80篇 |
2015年 | 63篇 |
2014年 | 72篇 |
2013年 | 111篇 |
2012年 | 156篇 |
2011年 | 190篇 |
2010年 | 103篇 |
2009年 | 85篇 |
2008年 | 151篇 |
2007年 | 125篇 |
2006年 | 102篇 |
2005年 | 128篇 |
2004年 | 67篇 |
2003年 | 62篇 |
2002年 | 57篇 |
2001年 | 21篇 |
2000年 | 12篇 |
1999年 | 18篇 |
1998年 | 24篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 11篇 |
1994年 | 5篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 10篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有2094条查询结果,搜索用时 15 毫秒
131.
Dr. Alberto Lena Dr. Alessandra Benassi Michele Stasi Christine Saint-Pierre Prof. Mauro Freccero Dr. Didier Gasparutto Dr. Sophie Bombard Prof. Filippo Doria Dr. Daniela Verga 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(35):e202200734
Combining the selectivity of G-quadruplex (G4) ligands with the spatial and temporal control of photochemistry is an emerging strategy to elucidate the biological relevance of these structures. In this work, we developed six novel V-shaped G4 ligands that can, upon irradiation, form stable covalent adducts with G4 structures via the reactive intermediate, quinone methide (QM). We thoroughly investigated the photochemical properties of the ligands and their ability to generate QMs. Subsequently, we analyzed their specificity for various topologies of G4 and discovered a preferential binding towards the human telomeric sequence. Finally, we tested the ligand ability to act as photochemical alkylating agents, identifying the covalent adducts with G4 structures. This work introduces a novel molecular tool in the chemical biology toolkit for G4s. 相似文献
132.
Dr. Chiara Platella Dr. Ettore Napolitano Dr. Claudia Riccardi Prof. Domenica Musumeci Prof. Daniela Montesarchio 《ChemistryOpen》2022,11(5):e202200090
DNA G-quadruplexes (G4s) are key structures for the development of targeted anticancer therapies. In this context, ligands selectively interacting with G4s can represent valuable anticancer drugs. Aiming at speeding up the identification of G4-targeting synthetic or natural compounds, we developed an affinity chromatography-based assay, named G-quadruplex on Oligo Affinity Support (G4-OAS), by synthesizing G4-forming sequences on commercially available polystyrene OAS. Then, due to unspecific binding of several hydrophobic ligands on nude OAS, we moved to Controlled Pore Glass (CPG). We thus conceived an ad hoc functionalized, universal support on which both the on-support elongation and deprotection of the G4-forming oligonucleotides can be performed, along with the successive affinity chromatography-based assay, renamed as G-quadruplex on Controlled Pore Glass (G4-CPG) assay. Here we describe these assays and their applications to the screening of several libraries of chemically different putative G4 ligands. Finally, ongoing studies and outlook of our G4-CPG assay are reported. 相似文献
133.
Aliona Ghendov-Mosanu Daniela Cojocari Greta Balan Antoanela Patras Ildiko Lung Maria-Loredana Soran Ocsana Opri Elena Cristea Rodica Sturza 《Molecules (Basel, Switzerland)》2022,27(5)
The article focuses on the optimization of the extraction process of biologically active compounds (BAC) from grape marc—a by-product of the wine industry. The influence of temperature, specifically 30 °C, 45 °C and 65 °C, and ethanol concentration in solutions, specifically 0–96% (v/v) on the extraction yield of polyphenols, flavonoids, tannins and anthocyanins, were investigated. The composition of individual polyphenols, anthocyanins and organic acids, antioxidant activity (DPPH and ABTS) and CIELab chromatic characteristics of the grape marc extracts (GME), were characterized. The microbiostatic and microbicidal effects in direct contact of GME with pathogenic microorganisms, Bacillus subtilis, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, were determined in vitro. The influence of extraction parameters on the total polyphenol content (TPC), total flavonoid content (TFC), tannin content (TC), total anthocyanin content (TAC) and their interdependencies were studied using information analysis. A mathematical model was developed on cubic spline functions. The analysis of individual compounds showed the presence of a wide range of flavonoids (procyanidin B2, procyanidin B1, hyperoside and quercetin), flavones (catechin), hydroxybenzoic acid derivatives (gallic, protocatechuic, p-hydroxybenzoic acids, m-hydroxybenzoic acid, syringic acid), hydroxycinic acid derivatives and ferulic acid methyl ester. The malvidol-3-glucoside was the main anthocyanin identified in the extract. A high amount of tartaric acid was also found. GME showed significant antimicrobial activity against Gram-positive bacteria and lower activity against Gram-negative bacteria. 相似文献
134.
Mihai Cosmin Corobea Oana Muhulet Florin Miculescu Iulian Vaile Antoniac Zina Vuluga Dorel Florea Dumitru Mircea Vuluga Maria Butnaru Daniela Ivanov Stefan Ioan Voicu Vijay Kumar Thakur 《先进技术聚合物》2016,27(12):1586-1595
In this study, a new class of heterogeneous membranes based on cellulose acetate (CA) polymer and a complex filler clay‐silica nanowires (SiO2NWs) was investigated for potential biomedical applications. SiO2NWs were synthesized using natural clay through a facile sol–gel method and were dispersed in the polymer solution by sonication in the 1.25, 2.5, and 5% weight ratio to the CA acetate polymer. Membranes were subsequently prepared via phase inversion by precipitation of the CA polymer in water. The pristine CA membrane and SiO2NWs based nanocomposites membranes were characterized using different characterization techniques. The presence of the SiO2NWs in the CA membrane was found to significantly enhance the protein retention, water wettability and thermal as well as mechanical properties in comparison to the pristine CA membrane. Water flows studies at different temperatures and the retention of bovine serum albumin have been studied and the nanocomposite membranes were found to exhibit superior performances compared with the pristine CA membranes. SiO2NWs‐CA membranes showed a much higher stability to the water temperature change during separation than CA membranes. Morphological changes clearly revealed that the composite membrane were much more compact than the pristine CA membranes. The rabbit dermal fibroblasts cell viability in cultures after 72 hr of incubation was found to be greater than 80%. These newly synthesized composite membranes exhibit a high potential to be used for various medical applications because of their non‐cytotoxic characteristics. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
135.
Daniela I. Bezuidenhout 《Journal of organometallic chemistry》2007,692(4):774-783
The binuclear alkoxycarbene complexes [M2(CO)9{C(OEt)C4H3Y}] (M = Mn, Y = S(1), O(2); Re, Y = S(3), O(4)) were synthesised and characterised, giving axial carbene ligands for the dimanganese complexes, and equatorial carbene ligands for the dirhenium complexes. Aminolysis of these complexes with ammonia and n-propylamine yielded complexes [M2(CO)9{C(NHR)C4H3Y}] (R = H, M = Mn, Y = S(5), O(6); Re, Y = S(7), O(8); R = propyl, M = Mn, Y = S(9), O(10); Re, Y = S(11), O(12)). For the smaller NH2-substituted carbene ligands, the X-ray structures determined showed equatorial carbene ligands for both dimanganese and dirhenium complexes, while the NHPr-substituted carbene complexes retained the original configurations of the precursor alkoxy carbene complex, indicating that the steric effects of both the M(CO)5-fragment and the carbene ligand substituent can affect the coordination site of the carbene ligands of Group VII transition metal complexes in the solid state. 相似文献
136.
Guella G Ascenzi D Franceschi P Tosi P 《Rapid communications in mass spectrometry : RCM》2007,21(20):3337-3344
The role of organic impurities in the methanol-to-olefin (MTO) industrial process catalyzed by zeolites is the subject of ongoing debate. We have found that methanol (HPLC and RPE grade) purchased from different chemical companies may contain organic impurities, whose ionization is the dominant process in the positive ion atmospheric pressure chemical ionization (APCI) spectrum of commercial CH(3)OH. Such impurities produce ions with elemental formulae C(n)H(2n+1)O(+) (n = 4, 5, 6); likewise, ionization of tetradeuterated methanol (CD(3)OD) leads to the corresponding fully deuterated series C(n)D(2n+1)O(+) (n = 4, 5, 6), an outcome which represents a clear evidence of their widespread diffusion. We suggest that their formation might be inherent to the chemical process whereby methanol is synthesized on an industrial scale. Mass spectrometry (MS) experiments, gas chromatography/mass spectrometry (GC/MS) analysis and nuclear magnetic resonance (NMR) measurements allowed us to establish that commercial methanol contains dimethyl acetals of simple alkyl ketones, such as propanone, butanone and pentanone. Ab initio calculations (DFT/B3LYP) proved useful to understanding the ionization mechanisms of such impurities. 相似文献
137.
Daniela Schlemmer E. R. de Oliveira M. J. Araújo Sales 《Journal of Thermal Analysis and Calorimetry》2007,87(3):635-638
Conventional plastics has a
large impact in increasing the environment’s pollution. That’s
why the interest has turned towards novel partially and completely biodegradable
polymers. In this work, blends of polystyrene and thermoplastic starch with
glycerol and Buriti (Mauritia flexuosa
L.) oil as plasticizers were prepared. Samples were analyzed using TG/DTG
and DSC techniques. The TG results indicated that the blends with Buriti oil
are thermally more stable than those with glycerol. The DSC analysis that
Buriti oil provides a higher degree of plasticization of PS, compared to the
blends plasticized using glycerol under the studied conditions. 相似文献
138.
139.
140.