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41.
Anna Rabe Julia Büker Dr. Soma Salamon Adarsh Koul Dr. Ulrich Hagemann Dr. Joachim Landers Dr. Klaus Friedel Ortega Dr. Baoxiang Peng Prof. Dr. Martin Muhler Prof. Dr. Heiko Wende Prof. Dr. Wolfgang Schuhmann Prof. Dr. Malte Behrens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17038-17048
By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co3O4, MgCo2O4, Co2FeO4, Co2AlO4 and CoFe2O4. The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H2O2 decomposition. Studying the effect of dominant surface termination, isotropic Co3O4 and CoFe2O4 catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co3+ plays the major role for high activity. In H2O2 decomposition, Co2+ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction. 相似文献
42.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
43.
Counting of Oxygen Defects versus Metal Surface Sites in Methanol Synthesis Catalysts by Different Probe Molecules
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Matthias B. Fichtl Julia Schumann Igor Kasatkin Nikolas Jacobsen Malte Behrens Robert Schlögl Martin Muhler Olaf Hinrichsen 《Angewandte Chemie (International ed. in English)》2014,53(27):7043-7047
Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N2O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N2O, temperature programmed desorption of H2, and kinetic experiments. The presence of ZnO dramatically influences the N2O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu‐ZnO interface and can be used to easily quantify the intensity of Cu‐Zn interaction. N2O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H2. 相似文献
44.
Dr. Sébastien Prévost Dr. Nathalie Dupré Markus Leutzsch Dr. Qinggang Wang Dr. Vijay Wakchaure Prof. Dr. Benjamin List 《Angewandte Chemie (International ed. in English)》2014,53(33):8770-8773
An asymmetric Torgov cyclization, catalyzed by a novel, highly Brønsted acidic dinitro‐substituted disulfonimide, is described. The reaction delivers the Torgov diene and various analogues with excellent yields and enantioselectivity. This method was applied in a very short synthesis of (+)‐estrone. 相似文献
45.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
46.
47.
The determination of sulfur in biologically relevant samples such as metalloproteins is described. The analytical methodology used is based on robust on-line coupling between capillary electrophoresis (CE) and octopole reaction cell inductively-coupled plasma mass spectrometry (ORC–ICP–MS). Polyatomic ions that form in the plasma and interfere with the determination of S at mass 32 are minimised by addition of xenon to the collision cell. The method has been applied to the separation and simultaneous element-specific detection of sulfur, cadmium, copper, and zinc in commercially available metallothionein preparations (MT) and metallothionein-like proteins (MLP) extracted from liver samples of bream (Abramis brama L.) caught in the river Elbe, Germany. Instrumental detection limits have been calculated according to the German standard procedure DIN 32645 for the determination of sulfur and some simultaneously measured trace elements in aqueous solution. For sulfur detection limits down to 1.3 g L–1 (34S) and 3.2 g L–1 (32S) were derived. For the other trace elements determined simultaneously detection limits ranging from 300 ng L–1 (58Ni) to 500 ng L–1 (66Zn, 55Mn) were achieved. For quantification of sulfur and cadmium in a commercially available MT preparation under hyphenated conditions the use of external calibration is suggested. Finally, the need for proper sample-preparation technique will be discussed. 相似文献
48.
Orval A. Mamer George Just Chun-Sing Li Patrice Préville Sara Watson Robert Young James A. Yergey 《Journal of the American Society for Mass Spectrometry》1994,5(4):292-298
Several acylating reagents are synthesized and used to introduce quatemary phosphonium or ammonium or ternary sulfonium functions into a simple model of a peptido leukotriene (PLT). One of these reagents was selected for further study with LTE4, LTD4, and LTC4. We demonstrate that acylation of the free amine function of PLTs to produce the 5-triphenylphosphoniumvaleryl-amide (TPPV) derivatives enhances chemical stabilities and significantly increases responses in fast-atom bombardment and continuous-flow liquid secondary ion mass spectrometry (CF-LSIMS) relative to the native PLTs. With high-performance liquid chromatography inlet to CF-LSIMS, we demonstrate the facile detection in selected ion monitoring of the TPPV derivative of 3 pg of LTD4. 相似文献
49.
Der Geometriefaktor von radioaktiven umschlossenen oder offenen Strahlenquellen hängt bei der Messung mittels einer Kernstrahlungsmeßsonde von der räumlichen Anordnung der Strahlenquelle zu der strahlenexponierten wirksamen Fläche des Detektors und von der Geometrie der Strahlenquelle selbst ab. Fūr punktförmige Strahler in verschiedenen Positionen, Geraden, Kreisflächen und Zylinder wurde in möglichst einheitlicher Vorgehensweise die Berechnung der Geometriefaktoren bezüglich kreisförmiger ebener Detektionsflächen vorgenommen und rechentechnisch in Form von BESM 6-Algolprogrammen realisiert. Die Berechnungsergebnisse sind untereinander konsistent und wurden möglichst durch unabhängige Verfahren oder experimentelle Werte kontrolliert. Die Rechengenauigkeit kann gemäß den vorliegenden Anforderungen frei gewählt werden. 相似文献
50.
Jaroslav Hron Josef Málek Vít Průša K.R. Rajagopal 《Nonlinear Analysis: Real World Applications》2011,12(1):394-402
Recently Suslov and Tran (2008) [1] claimed to have found an error in one of the solutions given in the paper by Hron (2001) et al. [2] concerning the flows of fluids with pressure-dependent viscosities. We show that their arguments are related to the question of the continuity of the pressure, and we show that the original solution, although it is not a classical one, can be interpreted as a solution in a generalized sense. Mathematical and physical implications of such generalizations are briefly discussed. The discussion in the paper highlights the importance of recognizing what is meant by a “solution” to a partial differential equation, whether by a solution we mean a classical solution, a weak solution, or a solution in some other sense. 相似文献