全文获取类型
收费全文 | 1416篇 |
免费 | 43篇 |
国内免费 | 10篇 |
专业分类
化学 | 903篇 |
晶体学 | 15篇 |
力学 | 54篇 |
数学 | 174篇 |
物理学 | 323篇 |
出版年
2023年 | 15篇 |
2022年 | 32篇 |
2021年 | 27篇 |
2020年 | 15篇 |
2019年 | 20篇 |
2018年 | 22篇 |
2017年 | 23篇 |
2016年 | 46篇 |
2015年 | 41篇 |
2014年 | 41篇 |
2013年 | 87篇 |
2012年 | 90篇 |
2011年 | 91篇 |
2010年 | 64篇 |
2009年 | 86篇 |
2008年 | 81篇 |
2007年 | 91篇 |
2006年 | 68篇 |
2005年 | 60篇 |
2004年 | 45篇 |
2003年 | 34篇 |
2002年 | 52篇 |
2001年 | 40篇 |
2000年 | 46篇 |
1999年 | 28篇 |
1998年 | 15篇 |
1997年 | 18篇 |
1996年 | 17篇 |
1995年 | 15篇 |
1994年 | 6篇 |
1993年 | 13篇 |
1992年 | 18篇 |
1991年 | 16篇 |
1990年 | 15篇 |
1989年 | 11篇 |
1988年 | 15篇 |
1987年 | 11篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1974年 | 3篇 |
1966年 | 1篇 |
1948年 | 3篇 |
1935年 | 1篇 |
排序方式: 共有1469条查询结果,搜索用时 15 毫秒
41.
Ana Salomé Pires João Batista Dina Murtinho Célia Nogueira Anna Karamysheva M. Luísa Ramos Bruce F. Milne Nuno Tiago Tavares José Gonçalves Ana Cristina Gonçalves Ana Margarida Abrantes Rui Soares Teresa Gonçalves Maria Filomena Botelho M. Elisa Silva Serra 《应用有机金属化学》2020,34(5):e5569
Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC50 of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment. 相似文献
42.
Ramos EL Mata-Gómez MA Rodríguez-Durán LV Belmares RE Rodríguez-Herrera R Aguilar CN 《Applied biochemistry and biotechnology》2011,165(5-6):1141-1151
Tannase is an inducible enzyme with important applications in the food and pharmaceutical industries. This enzyme was produced by the fungus Aspergillus niger GH1 under solid-state fermentation using polyurethane foam as solid support and tannic acid as sole carbon source and tannase inducer. Physicochemical properties of A. niger tannase were characterized, and the kinetic and thermodynamics parameters on methyl gallate hydrolysis were evaluated. The enzyme was stable in a pH range of 2-8 and a functional temperature range of 25-65 °C. The highest k(cat) value was 2,611.10 s(-1) at 65 °C. Tannase had more affinity for methyl gallate at 45 °C with a K(M) value of 1.82 mM and an efficiency of hydrolysis (k(cat)/K(M)) of 330.01 s(-1) mM(-1). The lowest E(a) value was found to be 21.38 kJ/mol at 4.4 mM of methyl gallate. The lowest free energy of Gibbs (ΔG) and enthalpy (ΔH) were found to be 64.86 and 18.56 kJ/mol, respectively. Entropy (ΔS) was -0.22 kJ/mol K. Results suggest that the A. niger GH1 tannase is an attractive enzyme for industrial applications due its catalytic and thermodynamical properties. 相似文献
43.
Page T Nguyen HT Hilts L Ramos L Hanrahan G 《Analytical and bioanalytical chemistry》2012,403(8):2367-2375
This work reveals a computational framework for parallel electrophoretic separation of complex biological macromolecules and model urinary metabolites. More specifically, the implementation of a particle swarm optimization (PSO) algorithm on a neural network platform for multiparameter optimization of multiplexed 24-capillary electrophoresis technology with UV detection is highlighted. Two experimental systems were examined: (1) separation of purified rabbit metallothioneins and (2) separation of model toluene urinary metabolites and selected organic acids. Results proved superior to the use of neural networks employing standard back propagation when examining training error, fitting response, and predictive abilities. Simulation runs were obtained as a result of metaheuristic examination of the global search space with experimental responses in good agreement with predicted values. Full separation of selected analytes was realized after employing optimal model conditions. This framework provides guidance for the application of metaheuristic computational tools to aid in future studies involving parallel chemical separation and screening. Adaptable pseudo-code is provided to enable users of varied software packages and modeling framework to implement the PSO algorithm for their desired use. 相似文献
44.
Zinc is the second most abundant transition element in biology and the only metal known to be represented in enzymes from each one of the six classes established by the International Union of Biochemistry. The flexible coordination geometry, the fast ligand exchange, the lack of redox activity, and its role as Lewis acid are just some of the features that make zinc an invaluable element in biological catalysis. In this study, we have analyzed the importance in mononuclear Zn enzymes of an interesting mechanistic phenomenon known as carboxylate shift, which is characterized by a change in the coordination mode of a carboxylate group (mono to bidentate or vice versa) with both ligand entrance or exit from the metal coordination sphere. Using B3LYP calculations, we were able to unveil in detail patterns relating the intrinsic characteristics of a given Zn coordination sphere with the existence or not of a carboxylate-shift mechanism and the additional energy stabilization arising from it. In particular, a specific Zn coordination sphere containing a carboxylate ligand (Asp or Glu), a cysteine, and a histidine has been shown to have the most favorable combination of amino acid residues that ensures a fast ligand exchange. 相似文献
45.
A classical Lewis adduct derives from a covalent bond between a Lewis acid and a base. When the adduct formation is precluded by means of steric hindrance the association of the respective acid-base molecular system is defined as a frustrated Lewis pair (FLP). In this work, the archetypal FLP Mes3P/B(C6F5)3 was characterized for the first time by resonance Raman spectroscopy, and the results were supported by density functional theory (DFT) calculations. The charge transfer nature of the lowest energy electronic transition, from phosphine to borane, was confirmed by the selective enhancement of the Raman bands associated to the FLP chromophore at resonance condition. Herein, we demonstrate the use of resonance Raman spectroscopy as a distinguished technique to probe the weak interaction involved in FLP chemistry. 相似文献
46.
47.
Ana Luiza Coeli Cruz Ramos Laiza Andrade Nogueira Mauro Ramalho Silva Ana Carolina do Carmo Mazzinghy Ana Paula Xavier Mariano Tssia Nunes de Albuquerque Rodrigues Ana Cardoso Clemente Filha Ferreira de Paula Angelita Cristine de Melo Rodinei Augusti Raquel Linhares Bello de Araújo Inayara Cristina Alves Lacerda Júlio Onsio Ferreira Melo 《Molecules (Basel, Switzerland)》2022,27(15)
Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min. 相似文献
48.
49.
J. A. Paixo A. Matos Beja M. Ramos Silva L. Alte da Veiga A. C. Serra 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(12):1501-1502
In the title compound, C8H5Br2NO4, the endocyclic angles of the ring deviate significantly from the ideal value of 120°. The substituents deviate from the plane of the ring, with large twist angles for the aldehyde, nitro and methoxy groups. The geometry of the molecule in the crystal is compared with that of the isolated molecule, as given by a self‐consistent field molecular‐orbital Hartree–Fock calculation. Only weak hydrogen bonds of the C—H?Br and C—H?O types are present in the crystal structure. 相似文献
50.
M. Ramos Silva A. Matos Beja J. A. Paixo L. Alte da Veiga A. J. F. N. Sobral A. M. d'A. Rocha Gonsalves 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(10):1263-1264
In the title compound, C16H17NO4, the benzyloxycarbonyl group is anti to the pyrrolic N atom. The molecules are joined into head‐to‐head dimers by hydrogen bonds involving the carboxylic acid groups. There is orientational disorder of these groups over two positions with approximately equal occupancy. A weaker hydrogen bond between the pyrrolic N atom and the carbonyl O atom of the benzyloxycarbonyl group joins the dimers into chains running parallel to the [110] direction. 相似文献