全文获取类型
收费全文 | 4728篇 |
免费 | 158篇 |
国内免费 | 20篇 |
专业分类
化学 | 2850篇 |
晶体学 | 22篇 |
力学 | 108篇 |
数学 | 787篇 |
物理学 | 630篇 |
无线电 | 509篇 |
出版年
2023年 | 43篇 |
2022年 | 105篇 |
2021年 | 118篇 |
2020年 | 75篇 |
2019年 | 103篇 |
2018年 | 81篇 |
2017年 | 84篇 |
2016年 | 182篇 |
2015年 | 150篇 |
2014年 | 194篇 |
2013年 | 263篇 |
2012年 | 412篇 |
2011年 | 466篇 |
2010年 | 266篇 |
2009年 | 275篇 |
2008年 | 323篇 |
2007年 | 280篇 |
2006年 | 255篇 |
2005年 | 225篇 |
2004年 | 216篇 |
2003年 | 143篇 |
2002年 | 104篇 |
2001年 | 48篇 |
2000年 | 42篇 |
1999年 | 55篇 |
1998年 | 27篇 |
1997年 | 24篇 |
1996年 | 32篇 |
1995年 | 12篇 |
1994年 | 19篇 |
1993年 | 17篇 |
1992年 | 24篇 |
1991年 | 14篇 |
1990年 | 23篇 |
1989年 | 10篇 |
1988年 | 13篇 |
1987年 | 11篇 |
1986年 | 14篇 |
1985年 | 22篇 |
1984年 | 23篇 |
1983年 | 10篇 |
1982年 | 8篇 |
1981年 | 15篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1974年 | 7篇 |
1971年 | 6篇 |
1970年 | 5篇 |
1963年 | 5篇 |
排序方式: 共有4906条查询结果,搜索用时 31 毫秒
991.
Jos S. Cmara Rosa Perestrelo Cristina V. Berenguer Carolina F. P. Andrade Telma M. Gomes Basit Olayanju Abuzar Kabir Cristina M. R. Rocha Jos Antnio Teixeira Jorge A. M. Pereira 《Molecules (Basel, Switzerland)》2022,27(9)
Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted. 相似文献
992.
Computational simulation of colloidal systems make use of empirical interaction potentials that are founded in well-established theory. In this work, we have performed parallel tempering Monte Carlo (PTMC) simulations to calculate heat capacity and to assess structural transitions, which may occur in charged colloidal clusters whose effective interactions are described by a sum of pair potentials with attractive short-range and repulsive long-range components. Previous studies on these systems have shown that the global minimum structure varies from spherical-type shapes for small-size clusters to Bernal spiral and “beaded-necklace” shapes at intermediate and larger sizes, respectively. In order to study both structural transitions and dissociation, we have organized the structures appearing in the PTMC calculations by three sets according to their energy: (i) low-energy structures, including the global minimum; (ii) intermediate-energy “beaded-necklace” motifs; (iii) high-energy linear and branched structures that characterize the dissociative clusters. We observe that, depending on the cluster, either peaks or shoulders on the heat–capacity curve constitute thermodynamics signatures of dissociation and structural transitions. The dissociation occurs at for all studied clusters and it is characterized by the appearance of a significant number of linear structures, while the structural transitions corresponding to unrolling the Bernal spiral are quite dependent on the size of the colloidal system. 相似文献
993.
甘油的催化选择氧化 总被引:2,自引:0,他引:2
综述了近年来生物柴油主要副产物甘油的催化选择氧化的研究进展。分析了甘油的化学催化选择氧化的反应网络;介绍了催化甘油选择氧化反应主要的催化剂如负载型金属催化剂、多孔催化剂以及有机酰基-TEMPO催化剂的催化性能及其催化机理;评述了甘油催化氧化过程中各反应条件等对产物选择性和反应物转化率的影响;概括了甘油的电催化氧化、甘油催化氧化聚合生成新型聚合物-聚丙酮二酸盐(Polyketomalonate)等新催化反应及其机理,总结了甘油生物催化氧化的产物二羟基丙酮(DHA)的新进展。最后提出了甘油的催化氧化存在的一些问题,并展望了甘油催化氧化的研究和发展方向。 相似文献
994.
Zuleima Blanco Esteban Fernandez-Moreira Michael R. Mijares Carmen Celis Gricelis Martínez Juan B. De Sanctis Soa Gursk Petr Dubk Marin Hajdch Ali Mijoba Yael García Xenn Serrano Nahum Herrera Jhonny Correa-Abril Yonathan Parra Jorge ngel Hegira Ramírez Jaime E. Charris 《Molecules (Basel, Switzerland)》2022,27(17)
The coexistence of leishmaniasis, Chagas disease, and neoplasia in endemic areas has been extensively documented. The use of common drugs in the treatment of these pathologies invites us to search for new molecules with these characteristics. In this research, we report 16 synthetic chalcone derivatives that were investigated for leishmanicidal and trypanocidal activities as well as for antiproliferative potential on eight human cancers and two nontumor cell lines. The final compounds 8–23 were obtained using the classical base-catalyzed Claisen–Schmidt condensation. The most potent compounds as parasiticidal were found to be 22 and 23, while compounds 18 and 22 showed the best antiproliferative activity and therapeutic index against CCRF-CEM, K562, A549, and U2OS cancer cell lines and non-toxic VERO, BMDM, MRC-5, and BJ cells. In the case of K562 and the corresponding drug-resistant K562-TAX cell lines, the antiproliferative activity has shown a more significant difference for compound 19 having 10.3 times higher activity against the K562-TAX than K562 cell line. Flow cytometry analysis using K562 and A549 cell lines cultured with compounds 18 and 22 confirmed the induction of apoptosis in treated cells after 24 h. Based on the structural analysis, these chalcones represent new compounds potentially useful for Leishmania, Trypanosoma cruzi, and some cancer treatments. 相似文献
995.
Jorge R. Virus-Segovia Fernando Reyes Sandra Ruíz Jesús Martín Ignacio Fernndez-Pastor Carlos Justicia Mercedes de la Cruz Caridad Díaz Thomas A. Mackenzie Olga Genilloud Ignacio Gonzlez Jos R. Tormo 《Molecules (Basel, Switzerland)》2022,27(19)
Current needs in finding new antibiotics against emerging multidrug-resistant superbugs are pushing the scientific community into coming back to Nature for the discovery of novel active structures. Recently, a survey of halophilic actinomyectes from saline substrates of El Saladar del Margen, in the Cúllar-Baza depression (Granada, Spain), led us to the isolation and identification of 108 strains from the rhizosphere of the endemic plant Limonium majus. Evaluation of the potential of these strains to produce new anti-infective agents against superbug pathogens was performed through fermentation in 10 different culture media using an OSMAC approach and assessment of the antibacterial and antifungal properties of their acetone extracts. The study allowed the isolation of two novel antibiotic compounds, kribbellichelin A (1) and B (2), along with the known metabolites sandramycin (3), coproporphyrin III (4), and kribelloside C (5) from a bioassay-guided fractionation of scaled-up active extracts of the Kribbella sp. CA-293567 strain. The structures of the new molecules were elucidated by ESI-qTOF-MS/MS, 1D and 2D NMR, and Marfey’s analysis for the determination of the absolute configuration of their amino acid residues. Compounds 1–3 and 5 were assayed against a panel of relevant antibiotic-resistant pathogenic strains and evaluated for cytotoxicity versus the human hepatoma cell line HepG2 (ATCC HB-8065). Kribbellichelins A (1) and B (2) showed antimicrobial activity versus Candida albicans ATCC-64124, weak potency against Acinetobacter baumannii MB-5973 and Pseudomonas aeruginosa MB-5919, and an atypical dose-dependent concentration profile against Aspergillus fumigatus ATCC-46645. Sandramycin (3) confirmed previously reported excellent growth inhibition activity against MRSA MB-5393 but also presented clear antifungal activity against C. albicans ATCC-64124 and A. fumigatus ATCC-46645 associated with lower cytotoxicity observed in HepG2, whereas Kribelloside C (5) displayed high antifungal activity only against A. fumigatus ATCC-46645. Herein, we describe the processes followed for the isolation, structure elucidation, and potency evaluation of these two new active compounds against a panel of human pathogens as well as, for the first time, the characterization of the antifungal activities of sandramycin (3). 相似文献
996.
Jelver A. Sierra Katherine Gilchrist Jorge H. Tabares-Guevara Liliana Betancur-Galvis Jose R. Ramirez-Pineda Miguel A. Gonzlez-Cardenete 《Molecules (Basel, Switzerland)》2022,27(19)
Abietic acid (AA), dehydroabietic acid (DHA) and triptoquinones (TQs) are bioactive abietane-type diterpenoids, which are present in many edible vegetables and medicinal herbs with health-promoting properties. Evidence suggests that beneficial effects of diterpenes operate, at least in part, through effects on cells in the immune system. Dendritic cells (DCs) are a key type of leukocyte involved in the initiation and regulation of the immune/inflammatory response and natural or synthetic compounds that modulate DC functions could be potential anti-inflammatory/immunomodulatory agents. Herein, we report the screening of 23 known semisynthetic AA and DHA derivatives, and TQs, synthesized previously by us, in a multi-analyte DC-based assay that detects inhibition of pro-inflammatory cytokine production. Based on the magnitude of the inhibitory effect observed and the number of cytokines inhibited, a variety of activities among compounds were observed, ranging from inactive/weak to very potent inhibitors. Structurally, either alcohol or methyl ester substituents on ring A along with the introduction of aromaticity and oxidation in ring C in the abietane skeleton were found in compounds with higher inhibitory properties. Two DHA derivatives and two TQs exhibited a significant inhibition in all pro-inflammatory cytokines tested and were further investigated. The results confirmed their ability to inhibit, dose dependently, LPS-stimulated expression of the co-stimulatory molecules CD40 and/or CD86 and the production of the pro-inflammatory cytokines IL-1β, IL-6, IL-12 and TNFα. Our results demonstrate that DC maturation process can be targeted by semisynthetic DHA derivatives and TQ epimers and indicate the potential of these compounds as optimizable anti-inflammatory/immunomodulatory agents. 相似文献
997.
Rolando Ramirez Carlos Eduardo Schnorr Jordana Georgin Matias Schadeck Netto Dison S. P. Franco Elvis Carissimi Delmira Wolff Luis F. O. Silva Guilherme Luiz Dotto 《Molecules (Basel, Switzerland)》2022,27(22)
Brazil’s production and consumption of açai pulp (Euterpe oleracea) occur on a large scale. Most of the fruit is formed by the pit, which generates countless tons of residual biomass. A new purpose for this biomass, making its consumption highly sustainable, was presented in this study, where activated carbon (AC) was produced with zinc chloride for later use as an adsorbent. AC carbon formed by carbon and with a yield of 28 % was satisfactorily used as an adsorbent in removing the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Removal efficiency was due to the highly porous surface (Vp = 0.467 cm3 g−1; Dp = 1.126 nm) and good surface área (SBET = 920.56 m2 g−1). The equilibrium data fit the Sips heterogeneous and homogeneous surface model better. It was observed that the increase in temperature favored adsorption, reaching a maximum experimental capacity of 218 mg g−1 at 328 K. The thermodynamic behavior indicated a spontaneous, favorable, and endothermic behavior. The magnitude of the enthalpy of adsorption was in agreement with the physical adsorption. Regardless of the herbicide concentration, the adsorbent displayed fast kinetics, reaching equilibrium within 120 min. The linear driving force (LDF) model provided a strong statistical match to the kinetic curves. AC with zinc chloride (ZnCl2), created from leftover açai biomass, is a potential alternative as an adsorbent for treating effluents containing 2,4-D. 相似文献
998.
999.
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
1000.
Anabela Martínez Jorge Cantero Antonio J. Melndez-Martínez Margot Paulino 《Molecules (Basel, Switzerland)》2022,27(22)
Carotenoids are isoprenoid pigments, and sources of vitamin A in humans. The first metabolic pathway for their synthesis is mediated by the enzymes β,β-carotene-15,15′-dioxygenase (BCO1) and β,β-carotene-9′,10′-dioxygenase (BCO2), which cleave carotenoids into smaller compounds, called apocarotenoids. The objective of this study is to gain insight into the interaction of BCO1 and BCO2 with carotenoids, adding structural diversity and importance in the agro-food and/or health sectors. Homology modeling of BCO1 and BCO2, and the molecular dynamics of complexes with all carotenoids were performed. Interaction energy and structures were analyzed. For both enzymes, the general structure is conserved with a seven beta-sheet structure, and the β-carotene is positioned at an optimal distance from the catalytic center. Fe2+ forms in an octahedral coordination sphere with four perfectly conserved histidine residues. BCO1 finds stability in a structure in which the β-carotene is positioned ready for enzymatic catalysis at the 15–15′ bond, and BCO2 in positioning the bond to be cleaved (C9–C10) close to the active site. In BCO1 the carotenoids interact with only seven residues with aromatic rings, while the interaction of BCO2 is much more varied in terms of the type of interaction, with more residues of different chemical natures. 相似文献