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211.
Aleksandra Wiśniewska Katarzyna Baranowska Rafał Grubba Eberhard Matern Jerzy Pikies Prof. Dr. 《无机化学与普通化学杂志》2010,636(8):1549-1556
tBu2P–PLi–PtBu2 · 2THF reacts with [(R3P)2MCl2] (M = Pt, Pd, Ni; R3P = Et3P, pTol3P, Ph2EtP, iPr3P) to yield isomers of [(1,2‐η‐tBu2P=P–PtBu2)M(PR3)Cl], in which the tBu2P–P–PtBu2 ligand adopts the arrangement of a side‐on bonded 1,1‐di‐tert‐butyl‐2‐(di‐tert‐butylphosphanyl)diphosphenium cation. tBu2P–PLi–P(NEt2)2 · 2THF reacts with [(R3P)2MCl2] but does not form complexes with a tBu2P–P–P(NEt2)2 moiety, however, splitting of a P–P(NEt2)2 bond of the parent triphosphane takes place. 相似文献
212.
Self-assembled monolayers of alpha-helical peptides on a gold surface were employed as model systems for the investigation of mediated electron transfer. The peptides contained 14, 15, 16, and 17 amino acid residues. The measurements of electron transmission through single molecules of helical peptides were performed using scanning tunneling spectroscopy (STS). The molecules were trapped between the gold tip and the substrate. Electrical contact between the molecule and the gold probe was achieved by the use of peptides containing thiol groups present at each end of the helix. The conductance behavior of the peptides was examined as a function of tip-substrate distance at fixed bias voltage. Measurements performed with peptides containing different numbers of amino acid residues indicate that the distance dependence of electron transmission through an alpha-helix is weaker than that through simple n-alkyl bridges. 相似文献
213.
Law M Greene LE Radenovic A Kuykendall T Liphardt J Yang P 《The journal of physical chemistry. B》2006,110(45):22652-22663
We describe the construction and performance of dye-sensitized solar cells (DSCs) based on arrays of ZnO nanowires coated with thin shells of amorphous Al(2)O(3) or anatase TiO(2) by atomic layer deposition. We find that alumina shells of all thicknesses act as insulating barriers that improve cell open-circuit voltage (V(OC)) only at the expense of a larger decrease in short-circuit current density (J(SC)). However, titania shells 10-25 nm in thickness cause a dramatic increase in V(OC) and fill factor with little current falloff, resulting in a substantial improvement in overall conversion efficiency, up to 2.25% under 100 mW cm(-2) AM 1.5 simulated sunlight. The superior performance of the ZnO-TiO(2) core-shell nanowire cells is a result of a radial surface field within each nanowire that decreases the rate of recombination in these devices. In a related set of experiments, we have found that TiO(2) blocking layers deposited underneath the nanowire films yield cells with reduced efficiency, in contrast to the beneficial use of blocking layers in some TiO(2) nanoparticle cells. Raising the efficiency of our nanowire DSCs above 2.5% depends on achieving higher dye loadings through an increase in nanowire array surface area. 相似文献
214.
Aleksandra Jeličić Franziska Köhler Alette Winter Sabine Beuermann 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):3188-3199
Pulsed laser polymerizations were used to study the propagation kinetics of hydroxypropyl methacrylate (HPMA) in ionic liquids (ILs) and common organic solvents. The functional monomer was chosen to investigate the complex interplay of all interactions between monomer molecules and between monomer and solvent molecules and to obtain a deeper understanding of the impact of these interactions. The solvent effect on the HPMA propagation rate coefficient (kp) was examined using a linear solvation energy relationship (LSER) based on Kamlet‐Taft solvatochromic parameters π*, α, and β. The results suggest that dipolarity/polarizability, associated with π*, and hydrogen bond–donating ability of the solvents, accounted for by α, majorly contribute to variations in kp. Hydrogen bond–accepting (electron pair donating) ability of the solvents (β parameter) is of much lesser importance. In addition, LSER enables the prediction of HPMA kp based on solvatochromic parameters of the solvents. The results suggest that interactions between the hydroxyl group of the monomer and the anion are dominant compared with classical hydrogen bonding between carbonyl and hydroxyl groups of the monomer units. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3188–3199, 2010 相似文献
215.
216.
The separation of two systems containing minimum boiling azeotropes (acetone—methanol and tetrahydrofuran (THF)—water) was performed using extractive distillation with a heavy boiling mixed entrainer consisting of two compounds. The entrainer constituents did not form new azeotropes with each other and with the components of the original mixture. An analysis of the mixed entrainer influence on the vapor-liquid equilibrium (VLE) and relative volatility provides an understanding of the cases in which the separation by extractive distillation (ED) in the presence of the mixed entrainer revealed energy benefits over their individual constituents. New results for application of the mixed entrainer monoethanolamine (MEA)—ethylene glycol (EG) and dimethyl-sulphoxide (DMSO)—glycerol for the separation of THF—water and acetone—methanol, respectively, are presented for the first time. The individual selective agents were chosen from the efficient entrainers discussed in the literature. The calculations were performed using the platform Aspen Plus 7.3. Different extractive distillation flowsheets are provided for the zeotropic mixed agents, viz. with two or three columns. For the ED of the binary mixtures investigated, the structures of the different separation schemes, the operating parameters of the columns, and the energy consumptions are presented and compared. The application of the mixed entrainer MEA—EG fed into the ED column with pre-mixing can be recommended, providing up to 1.7 % of energy saving for acetone—methanol separation. In the case of THF—water, the mixed entrainer DMSO—glycerol provides 0.8 % of energy saving. The separate inputs of the individual constituents of the mixed entrainer led to a significant increase in the energy consumptions of the flowsheet because of the third regeneration column, hence this flowsheet cannot be recommended for use in the separation of both mixtures. 相似文献
217.
Summary From plant material (Allium sativum, Allium cepa, Allium porrum), extracts characterised by a high haemolytic activity were obtained. In the raw saponin preparation the percentage of saponins in garlic, onion and leek was determined, applying the densitometric method on thin layer chromatograms, previously proposed5. Purified crystalline or oil-like saponin preparations were hydrolysed or complexed with cholesterol. The isolated sapogenins were identified by mass spectrometry, IR, NMR and UV analysis. The following sapogenins were found: sitosterol, gitogenin, oleanolic acid and amyrin.
Mikrobestimmung von Steroid- und Triterpen-Saponinen in verschiedenem Pflanzenmaterial
Summary Aus Allium sativum, Allium cepa und Allium porrum wurden Extrakte erhalten, die stark hämolytisch wirken. Die rohen Saponin-Präparate wurden auf Dünnschicht-Platten mit unserer densitometrischen Methode untersucht und ihr Saponingehalt bestimmt. Die gereinigten, kristallisierten oder öligen Saponinpräparate wurden einer Hydrolyse und einer Komplexierung mit Cholesterin unterzogen. Die isolierten Sapogenine wurden massenspektrometrisch, mit IR, NMR und UV geprüft. Folgende Sapogenine wurden gefunden: Sitosterol, Gitogenin, Oleanolsäure und Amyrin.相似文献
218.
Once considered as mere curiosities, acyl metalloids are now recognized for their utility in enabling chemical synthesis. This perspective considers the reactivity displayed by acylboron, -silicon, -germanium, and tellurium species. By highlighting the role of these species in various transformations, we demonstrate how differences between the comprising elements result in varied reaction outcomes. While acylboron compounds are primarily used in polar transformations, germanium and tellurium species have found utility as radical precursors. Applications of acylsilanes are comparatively more diverse, owing to the possibility to access both radical and polar chemistry.Originally considered as fundamental curiosities, acyl metalloids have proven to be useful tools in synthesis. This perspective aims to highlight the modes of reactivity accessible to boron, silicon, germanium and tellurium species. 相似文献
219.
The palladium-catalyzed heteroannulation of N-carbobenzyloxy-o-iodoanilines with 1-phenylthio-1,3-butadiene afforded indolines 7, which were oxidized with DDQ to produce vinylogous 2-(phenylthio)indoles 8. The latter compounds underwent highly regioselective Diels-Alder cycloadditions with methyl propiolate in the presence of MeAlCl(2) or AlCl(3), with simultaneous elimination of benzenethiol, to afford methyl N-(carbobenzyloxy)carbazole-3-carboxylates 9 and, in some cases, the N-deprotected derivatives 11. This is the opposite regiochemistry of that observed previously with the corresponding sulfone analogues of 8. Thus, the regiochemistry of the cycloaddition can be effectively controlled by appropriate choice of oxidation state of the diene sulfur substituent. 相似文献
220.
Snežana S. Mitić Gordana Ž. Miletić Aleksandra N. Pavlović Snežana B. Tošić Dragan S. Velimirović 《中国化学会会志》2007,54(1):47-54
A kinetic method for the determination of micro quantities of amino acid arginine (Arg) is described in this paper. The catalytic activity of cobalt in the reaction of oxidation of purpurin (1,2,4‐trihydroxy‐antraquinone, PP) by hydrogen peroxide in alkaline buffer solution decreases in the presence of micro quantities of arginine, because of the formation of the complex. Operating conditions for the successful determination of arginine were optimized. The optimized conditions yielded a theoretical detection limit of 1.45 μg mL?1. Kinetic equations are proposed for the investigated process. The interference effects of certain foreign ions and amino acids upon the reaction rate were studied and removed in order to assess the selectivity of the method. The developed procedure was successfully applied to the determination of arginine in various pharmaceutical samples. The typical feature of this procedure is that determination can be carried out at room temperature and in a short analysis time. The newly developed method is simple, inexpensive and efficient for use in the analysis of a large number of samples. 相似文献