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561.
Lidong Li Clara S. B. Gomes Cludia A. Figueira Pedro T. Gomes M. Teresa Duarte 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(2):m110-m114
Two conformational polymorphs of trans‐chlorido(phenyl)bis(triphenylphosphine)nickel(II), [Ni(C6H5)Cl(C18H15P)2], (1), viz. orange needle‐shaped crystals (form I) and brown prism‐shaped crystals (form II), were obtained under different crystallization conditions from a mixture of toluene and n‐hexane, and characterized by single‐crystal X‐ray diffraction at low temperature. These two forms were compared with that published previously [Zeller, Herdtweck & Strassner (2003). Eur. J. Inorg. Chem. pp. 1802–1806], characterized at room temperature. Additionally, blue–green prisms of a 1:1 cocrystal of complex (1) with chloridobis(triphenylphosphine)nickel(I), (2), viz.trans‐chlorido(phenyl)bis(triphenylphosphine)nickel(II)–chloridobis(triphenylphosphine)nickel(I) (1/1), [Ni(C6H5)Cl(C18H15P)2]·[NiCl(C18H15P)2], (3), were obtained concomitantly with form I. In forms I and II, as well as in the cocrystal, the overall crystal packings are determined by an energetic interplay between intramolecular torsions and weak intermolecular C—H...π and C—H...Cl interactions. 相似文献
562.
Farràs P Teixidor F Rojo I Kivekäs R Sillanpää R González-Cardoso P Viñas C 《Journal of the American Chemical Society》2011,133(41):16537-16552
A series of monoansa [μ-1,1'-PR-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) and diansa [8,8'-μ-(1',2'-benzene)-μ-1,1'-PR-3,3'-Co(1,2-C(2)B(9)H(9))(2)](-) (R = Ph, (t)Bu) cobaltabisdicarbollidephanes have been synthesized, characterized and studied by NMR, MALDI-TOF-MS, UV-visible spectroscopy, cyclic voltammetry, and DFT calculations. Single crystal X-ray diffraction revealed a highly relaxed structure characterized by the title angle α of 3.8° ([7](-)), this being the smallest angle α for a metallacyclophane. In such compounds, the metal-to-phosphorus distance is less than the sum of their van der Waals radii. The availability of a phosphorus lone pair causes an electron delocalization through the metal, as shown by the abnormal (31)P NMR chemical shift. Remarkably, the combination of a phosphine donor and a phenyl acceptor moieties causes a synergistic effect that is observed through the different techniques used in this study. The importance of having an available lone pair is demonstrated by the oxidation of phosphorus with hydrogen peroxide, sulfur, and elemental black selenium to produce the corresponding P(V) compounds. When the electron lone pair is used to form the bond with the corresponding chalcogen atom, the communication between the donor and acceptor moieties on the diansa metallacyclophane is shut down. 相似文献
563.
Regalado EL Menendez R Valdés O Morales RA Laguna A Thomas OP Hernandez Y Nogueiras C Kijjoa A 《Natural product communications》2012,7(1):47-50
The aqueous ethanol extract of Thalassia testudinum leaves (BM-21) is now being developed in Cuba as an herbal medicine due to its promising pharmacological properties. Although some interesting biological activities of BM-21 have already been reported, its chemical composition remains mostly unknown. Thus, we now describe the qualitative and quantitative analyzes of BM-21 using standard phytochemical screening techniques, including colorimetric quantification, TLC and HPLC analyses. Phytochemical investigation of BM-21 resulted in the isolation and identification of a new phenolic sulfate ester (1), along with ten previously described phenolic derivatives (2-11), seven of which have never been previously reported from the genus Thalassia. The structures of these compounds were established by analysis of their spectroscopic (1D and 2D NMR) and spectrometric (HRMS) data, as well as by comparison of these with those reported in the literature. Furthermore, BM-21 was found to exhibit strong antioxidant activity in four different free radical scavenging assays (HO*, RO2*, O2-* and DPPH*). Consequently, this is the first study which highlights the phytochemical composition of BM-21 and demonstrates that this product is a rich source of natural antioxidants with potential applications in pharmaceutical, cosmetic and food industries. 相似文献
564.
Francisco Torrens Clara M. Gómez Isidro S. Monzó Concepción Abad Agustín Campos 《Macromolecular Symposia》2012,311(1):49-56
Summary: A model developed by Balazs' group to explain the phase behaviour of polymer/clay composites is extended to obtain an expression for the free energy of polymer/thin disc mixtures. Phase diagrams for monomer/disc mixtures are built by minimizing the free energy and calculating the chemical potentials of the three system components. Via the comparison of the diagrams, it is studied the effects of nanodisc size and interaction parameters on mixture stability and attained morphology. The performed predictions between monomers and discs give criteria that advance the properties of the mixture. Changes in monomer concentration and interaction parameters provide a means to prevent van der Waals-induced agglomeration. The model takes into account, in only a rather approximate manner, the long-range interactions between clay sheets. 相似文献
565.
Matabosch X Pozo OJ Pérez-Mañá C Farré M Marcos J Segura J Ventura R 《Analytical and bioanalytical chemistry》2012,404(2):325-340
Budesonide (BUD) is a glucocorticoid widely used for the treatment of asthma, rhinitis, and inflammatory bowel disease. Its use in sport competitions is prohibited when administered by oral, intravenous, intramuscular, or rectal routes. However, topical preparations are not prohibited. Strategies to discriminate between legal and forbidden administrations have to be developed by doping control laboratories. For this reason, metabolism of BUD has been re-evaluated using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with different scan methods. Urine samples obtained after oral administration of 3?mg of BUD to two healthy volunteers have been analyzed for metabolite detection in free and glucuronide metabolic fractions. Structures of the metabolites have been studied by LC-MS/MS using collision induced dissociation and gas chromatography-mass spectrometry (GC/MS) in full scan mode with electron ionization. Combination of all structural information allowed the proposition of the most comprehensive picture for BUD metabolism in humans to this date. Overall, 16 metabolites including ten previously unreported compounds have been detected. The main metabolite is 16α-hydroxy-prednisolone resulting from the cleavage of the acetal group. Other metabolites without the acetal group have been identified such as those resulting from reduction of C20 carbonyl group, oxidation of the C11 hydroxyl group and reduction of the A ring. Metabolites maintaining the acetal group have also been identified, resulting from 6-hydroxylation (6α and 6β-hydroxy-budesonide), 23-hydroxylation, reduction of C6-C7, oxidation of the C11 hydroxyl group, and reduction of the C20 carbonyl group. Metabolites were mainly excreted in the free fraction. All of them were excreted in urine during the first 24?h after administration, and seven of them were still detected up to 48?h after administration for both volunteers. 相似文献
566.
C Brieke F Rohrbach A Gottschalk G Mayer A Heckel 《Angewandte Chemie (International ed. in English)》2012,51(34):8446-8476
Spatial and temporal control over chemical and biological processes plays a key role in life, where the whole is often much more than the sum of its parts. Quite trivially, the molecules of a cell do not form a living system if they are only arranged in a random fashion. If we want to understand these relationships and especially the problems arising from malfunction, tools are necessary that allow us to design sophisticated experiments that address these questions. Highly valuable in this respect are external triggers that enable us to precisely determine where, when, and to what extent a process is started or stopped. Light is an ideal external trigger: It is highly selective and if applied correctly also harmless. It can be generated and manipulated with well-established techniques, and many ways exist to apply light to living systems-from cells to higher organisms. This Review will focus on developments over the last six years and includes discussions on the underlying technologies as well as their applications. 相似文献
567.
Lau CB Cheng L Cheng BW Yue GG Wong EC Lau CP Leung PC Fung KP 《Natural product research》2012,26(15):1446-1450
Hedyotis diffusa Willd. and Hedyotis corymbosa (L.) Lam. are closely related species of Rubiaceae family and they can be easily confused. Although previous reports have been found in which ultraviolet spectrum, convolution spectrometry or X-ray diffraction are reported to be used for distinguishing between the two species, these methods require specialised equipment. Hence, this study aims to develop a simple chromatographic method for the purpose. Our results illustrate the use of a thin-layer chromatographic (TLC) profile to differentiate between the two species, with a blue zone appearing at around an R(f) of 0.36 in H. corymbosa but not in H. diffusa. The compound corresponding to this blue zone was later found to be hedyotiscone A. LC-MS with multiple reaction monitoring was used as a tool to identify and quantify hedyotiscone A in the test samples. In conclusion, a quick and simple TLC assay was conducted to distinguish between the two species H. diffusa and H. corymbosa. 相似文献
568.
Patricia González‐Cardoso Anca‐Iulia Stoica Dr. Pau Farràs Dr. Ariadna Pepiol Clara Viñas Prof. Dr. Francesc Teixidor Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(22):6660-6665
The first artificially made set of electron acceptors is presented that are derived from a unique platform Cs[3,3′‐Co(C2B9H11)2], for which the redox potential of each differs from its predecessor by a fixed amount. The sequence of electron acceptors is made by substituting one, two, or more hydrogen atoms by chlorine atoms, yielding Cs[3,3′‐Co(C2B9H11?yCly)(C2B9H11?zClz)]. The higher the number of chlorine substituents, the more prone the platform is to be reduced. The effect is completely additive, so if a single substitution implies a reduction of 0.1 V of the redox potential of the parent complex, then ten substitutions imply a reduction of 1 V. 相似文献
569.
Rachel Serrano Víctor Gonzlez-Menndez Germn Martínez Clara Toro Jesús Martín Olga Genilloud
Jos R. Tormo 《Molecules (Basel, Switzerland)》2021,26(14)
Microbial natural products are an invaluable resource for the biotechnological industry. Genome mining studies have highlighted the huge biosynthetic potential of fungi, which is underexploited by standard fermentation conditions. Epigenetic effectors and/or cultivation-based approaches have successfully been applied to activate cryptic biosynthetic pathways in order to produce the chemical diversity suggested in available fungal genomes. The addition of Suberoylanilide Hydroxamic Acid to fermentation processes was evaluated to assess its effect on the metabolomic diversity of a taxonomically diverse fungal population. Here, metabolomic methodologies were implemented to identify changes in secondary metabolite profiles to determine the best fermentation conditions. The results confirmed previously described effects of the epigenetic modifier on the metabolism of a population of 232 wide diverse South Africa fungal strains cultured in different fermentation media where the induction of differential metabolites was observed. Furthermore, one solid-state fermentation (BRFT medium), two classic successful liquid fermentation media (LSFM and YES) and two new liquid media formulations (MCKX and SMK-II) were compared to identify the most productive conditions for the different populations of taxonomic subgroups. 相似文献
570.
Cosmin Copot Yu Zhong Clara M. Ionescu Robin De Keyser 《Central European Journal of Physics》2013,11(6):702-713
In this paper, two methods to tune a fractional-order PI λ D μ controller for a mechatronic system are presented. The first method is based on a genetic algorithm to obtain the parameter values for the fractionalorder PI λ D μ controller by global optimization. The second method used to design the fractional-order PI λ D μ controller relies on an auto-tuning approach by meeting some specifications in the frequency domain. The real-time experiments are conducted using a Steward platform which consists of a table tilted by six servo-motors with a ball on the top of the table. The considered system is a 6 degrees of freedom (d.o.f.) motion platform. The feedback on the position of the ball is obtained from images acquired by a visual sensor mounted above the platform. The fractional-order controllers were implemented and the performances of the steward platform are analyzed. 相似文献