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941.
This study sets out a comprehensive characterization of bulk Pd and Pd (ca. 8% w/w) supported on activated carbon (AC), graphite and graphitic nanofibers (GNF). Catalyst activation has been examined by temperature programmed reduction (TPR) analysis and the activated catalysts analyzed in terms of BET area, TEM, H2 chemisorption/TPD, and XRD measurements. While H2 chemisorption and TEM delivered the same sequence of increasing (surface area weighted) average Pd particle sizes, a significant difference (by up to a factor of 3) in the values obtained from both techniques has been recorded and is attributed to an unwarranted (but widely adopted) assumption of an exclusive H2/Pd adsorption stoichiometry=1/2. It is demonstrated that TEM analysis provides a valid mean particle size once it is established that the associated standard deviation is small and insensitive to additional particle counting. XRD line broadening yielded an essentially equivalent Pd size (20-25 nm) for each supported catalyst. The nature of the hydrogen associated with the supported catalysts has been probed and is shown to comprise of chemisorbed (on Pd), spillover (on the carbon support), and hydride (associated with Pd) species. Physical mixtures of bulk Pd + support (AC, graphite, and GNF) were also considered in order to assess hydrogen spillover by H2 TPD analysis. Generation of spillover hydrogen at room temperature is established where temperatures in excess of 740 K are required for effective desorption from the supported Pd catalysts, i.e., 280 K higher than that required for the desorption of chemisorbed hydrogen. Pd hydride formation (at room temperature) is shown to be reversible with decomposition occurring at ca. 380 K. Taking the hydrodechlorination of chlorobenzene as a test reaction, the capability of Pd hydride to promote a hydrogen scission of C-Cl in the absence of an external supply of H2 is demonstrated with a consequent consumption of the hydride. This catalytic response was entirely recoverable once the Pd hydride was replenished during a subsequent reactivation step. 相似文献
942.
Mondini S Cenedese S Marinoni G Molteni G Santo N Bianchi CL Ponti A 《Journal of colloid and interface science》2008,322(1):173-179
Magnetite nanoparticles covered by a layer of omega-hydroxycarboxylic acid were synthesized in one step by high-temperature decomposition of iron(III) omega-hydroxycarboxylates in tri- and tetra-ethylene glycol. The nanoparticles were characterized by TEM, XRD, IR, XPS and NMR techniques in order to show that they comprise a crystalline magnetite core and actually bear on the outer surface terminal hydroxy groups. The latter ones are convenient "handles" for further functionalization as opposed to the chemically-inert aliphatic chains which cover conventionally synthesized nanoparticles. This was shown by several examples in which the hydroxy groups on the nanoparticle surface were easily transformed in other functional groups or reacted with other molecules. For instance, the hydroxyl-decorated nanoparticles were made water soluble by esterification with a PEGylated acetic acid. The reactive behavior of the surfactant monolayer was monitored by degrading the nanoparticles with aqueous acid and isolating the surfactant for NMR characterization. In general, the reactivity of the terminal hydroxyl groups on the nanoparticle surface parallels that observed in the free surfactants. The reported hydroxyl-decorated magnetite nanoparticles can be thus considered as pro-functional nanoparticles, i.e., a convenient starting material to functionalized magnetic nanoparticles. 相似文献
943.
Stefania De Montis Claudia Fattuoni Enzo Cadoni Maria G. Cabiddu Michele Usai Salvatore Cabiddu 《Journal of heterocyclic chemistry》2008,45(5):1445-1449
944.
The Suzuki-Miyaura cross-coupling protocol was applied to the synthesis of 1a, the C-glycoside analogue of PsA methyl ether. This marks the first construction of a C-glycoside for this class of marine natural products, thereby offering an opportunity to compare its bioactivity to the natural substances. Its activity profile resembled that of PsA (1) and PsA O-methyl ether (1b) when assayed for its anti-inflammatory activity and its ability to inhibit phagocytosis. We conclude that the intact structure is present when a pseudopterosin expresses its anti-inflammatory and phagocytosis inhibitory properties and that they are, therefore, not likely to be prodrugs. Results show that 1a is an effective binding agent toward the A2A and A3 adenosine receptors, displaying IC50 values of 20 and 10 microM, respectively. 相似文献
945.
Claudia Dietze Claudia Hackl Renata Gerhardt Stephan Seim Detlev Belder 《Electrophoresis》2016,37(10):1345-1352
In this study, we present the coupling of chip‐based electrochromatography to MS using a glass chip with a monolithically integrated nanoelectrospray emitter. As separation column, an acrylate‐based porous polymer monolith is implemented into the glass chip by photopolymerization. For the establishment and development of this method, we used a test mixture detectable with both fluorescence and ESI‐MS. After successful evaluation of the approach with the test solutes, it was applied exemplarily for drug analysis such as high‐speed separations of benzodiazepines in pharmaceuticals. 相似文献
946.
Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy
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Claudia S. Gutsche Marlene Ortwerth Dr. Susanna Gräfe Keith J. Flanagan Prof. Mathias O. Senge Prof. Hans‐Ulrich Reissig Prof. Nora Kulak Dr. Arno Wiehe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13953-13964
The application of porphyrinoids in biomedical fields, such as photodynamic therapy (PDT), requires the introduction of functional groups to tune their solubility for the biological environment and to allow a coupling to other active moieties or carrier systems. A valuable motif in this regard is the pentafluorophenyl (PFP) substituent, which can easily undergo a regiospecific nucleophilic replacement (SNAr) of its para‐fluorine atom by a number of nucleophiles. Here, it is shown that, instead of amino‐substitution on the final porphyrinoid or BODIPY (boron dipyrromethene), the precursor 5‐(PFP)‐dipyrrane can be modified with amines (or alcohols). These dipyrranes were transformed into amino‐substituted BODIPYs. Condensation of these dipyrranes with aldehydes gave access to trans‐A2B2‐porphyrins and trans‐A2B‐corroles. By using pentafluorobenzaldehyde, it was possible to introduce another para‐fluorine atom, which enabled the synthesis of multifunctionalized tetrapyrroles. Furthermore, alkoxy‐ and amino‐substituted dipyrranes were applied to the synthesis of A3B3‐hexaphyrins. The polar porphyrins that were prepared by using this method exhibited in vitro PDT activity against several tumor cell lines. 相似文献
947.
Janine Richter Saioa Elordui-Zapatarietxe Håkan Emteborg Ina Fettig Julie Cabillic Enrica Alasonati Fanny Gantois Claudia Swart Taner Gokcen Murat Tunc Burcu Binici Andres Rodriguez-Cea Tea Zuliani Adriana Gonzalez Gago Daniel Pröfrock Marjaana Nousiainen George Sawal Mirella Buzoianu Rosemarie Philipp 《Accreditation and quality assurance》2016,21(2):121-129
The European Water Framework Directive 2000/60/EC requires monitoring of organic priority pollutants in so-called whole water samples, i.e. in aqueous non-filtered samples that contain natural colloidal and suspended particulate matter. Colloids and suspended particles in the liquid phase constitute a challenge for sample homogeneity and stability. Within the joint research project ENV08 “Traceable measurements for monitoring critical pollutants under the European Water Framework Directive 2000/60/EC”, whole water test materials were developed by spiking defined amounts of aqueous slurries of ultra-finely milled contaminated soil or sediment and aqueous solutions of humic acid into a natural mineral water matrix. This paper presents the results of an European-wide interlaboratory comparison (ILC) using this type of test materials. Target analytes were tributyltin, polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in the ng/L concentration range. Results of the ILC indicate that the produced materials are sufficiently homogeneous and stable to serve as samples for, e.g. proficiency testing or method validation. To our knowledge, this is the first time that ready-to-use water materials with a defined amount of suspended particulate and colloidal matter have been applied as test samples in an interlaboratory exercise. These samples meet the requirements of the European Water Framework Directive. Previous proficiency testing schemes mainly employed filtered water samples fortified with a spike of the target analyte in a water-miscible organic solvent. 相似文献
948.
Benjamin Schwarz Dr. Johannes Forster McKenna K. Goetz Duygu Yücel Claudia Berger Prof. Dr. Timo Jacob Prof. Dr. Carsten Streb 《Angewandte Chemie (International ed. in English)》2016,55(21):6329-6333
Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn4V4O17(OAc)3]3?. The compound is based on a [Mn4O4]6+ cubane core, which catalyzes the homogeneous, visible‐light‐driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V4O13]6? polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)3]2+ and the oxidant persulfate, visible‐light‐driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s?1 is observed. Electrochemical, mass‐spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water‐oxidation catalysts. 相似文献
949.
Back Cover: Visible‐Light‐Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster (Angew. Chem. Int. Ed. 21/2016)
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950.
Dr. Samuel Dessources Dr. Claudia Morais Dr. Têko W. Napporn Prof. K. Boniface Kokoh 《Chemphyschem》2016,17(23):3964-3973
Hydrogen oxidation and evolution reactions (HOR and HER) are studied on PtxNi1?x/C materials synthesized by the bromide anion exchange method. Physicochemical characterization shows that this surfactant‐free method enables the preparation of well‐dispersed and effective catalysts for the processes involved in the anode of H2/O2 fuel cells (HOR) and the cathode of water electrolyzers (HER). The Pt‐based materials are modified with different Ni contents to decrease the amount of costly precious metal in the electrode materials. These modified Pt‐based materials are found to be electroactive for both reactions without additional overpotential. Kinetic parameters such as the Tafel slope, exchange (j0) and kinetic current densities, and the rate‐determining steps of the reaction mechanisms are determined for each Pt–Ni catalyst and compared to those obtained at the Pt/C surface in alkaline medium. The high j0 values that are obtained indicate a probable contribution of the surface structure of the catalysts due to their roughness and the presence of oxygenated Ni species even at low potentials. 相似文献