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1.
Monte Carlo simulations have been performed to explore the solution structure of ethyl, isopropyl, isobutyl, and tertiary butyl alcohols in pure water, pure acetonitrile, and different mixtures of the two solvents. The explicit solvent studies in NpT ensembles at T = 298 K illustrate that the solute "discriminates" the solvent's components and that the composition of the first solvation shell differs from that of the bulk solution. Since the polarizable continuum dielectric method (PCM) does not presently model the solvation of molecules with both polar and apolar sites in mixed protic solvents, we suggest a direction for further program development wherein a continuum dielectric method would accept more than one solvent and the solute sites would be solvated by user-defined solvent components. The prevailing solvation model will be determined upon the lowest free energy calculated for a particular solvation pattern of the solute having a specific conformational/tautomeric state. Characterization of equilibrium hydrogen-bond formation becomes a complicated problem that depends on the chemical properties of the solute and its conformation, as well as upon the varying nature of the first solvation shell. For example, while the number of hydrogen bonds to secondary and tertiary alcohol solutes are nearly constant in pure water and in water-acetonitrile mixtures with at least 50% water content, the number of hydrogen bonds to primary alcohols gradually decreases for most of their conformations when acetonitrile content is increased. Nonetheless, the calculations indicate that O-H...O(water) hydrogen bonds are still possible in a small fraction of the arrangements for the solution models with water content of 30% or less. The isopentene solute does not form any observable hydrogen bonds, despite having an electron-rich, double-bond site. 相似文献
2.
Valdas Laurinavicius Julija Razumiene Bogumila Kurtinaitiene Ingrida Lapenaite Irina Bachmatova Liucija Marcinkeviciene Rolandas Meskys Arunas Ramanavicius 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,55(1-2):29-32
This paper focuses on the use of PQQ-dependent enzymes (PQQ enzymes) in amperometrical biosensors and gives emphasis on their innovative designs and applications. The study covers some aspects in the evolution of biosensors based on PQQ enzymes. Main attention is focused on the electrochemical properties of PQQ enzymes as very promising materials for the formation of electrochemical biosensors. Immobilization approaches and redox mediators recently used in PQQ enzymes based biosensors are reviewed. The acceptance of polypyrrole as a very promising immobilization matrix for some PQQ enzymes is discussed. 相似文献
3.
Gucek M Makuc S Mlakar A Bericnik-Vrbovsek J Marsel J 《Rapid communications in mass spectrometry : RCM》2002,16(12):1186-1191
For the determination of glutathione (GSH) and its oxidized form (GSSG) in spruce needles their electrospray mass and MS/MS spectra were recorded with an ion trap mass spectrometer (ITMS, LCQ, Finnigan) and a triple stage quadrupole mass spectrometer (TSQ, Quattro II, Micromass). A study of the stability of GSH in aqueous solutions shows the presence of dimeric and trimeric forms of GSH, as well as GSSG, GSH-sulfonate and GSH-sulfinic acid. The same components were also found in extracts of spruce needles. We developed an assay which is suitable for monitoring low concentrations of GSH and similar compounds in plant tissues, employing the sensitivity and specificity of LC/MS/MS. Preliminary results on the mass spectrometric determination of GSH in spruce needles are given. 相似文献
4.
5.
Dipl.‐Chem. Sascha A. Erhardt Dr. Florian Hoffmann Dr. Jürgen O. Daiß Dr. Jürgen Stohrer Dr. Eberhardt Herdtweck Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(15):4818-4825
(Acetoxymethyl)silanes 2 , 7 a – c , and 10 a – c with at least one alkoxy group, of the general formula (AcOCH2)Si(OR)3?n(CH3)n (R: Me, Et, iPr; n=0, 1, 2), were synthesized from the corresponding (chloromethyl)silanes 1 , 6 a – c , and 9 a – c by treatment with potassium acetate under phase‐transfer‐catalysis conditions. These compounds were found to provide 2,2,5,5‐organo‐substituted 1,4‐dioxa‐2,5‐disilacyclohexanes 3 , 8 a – c , and 11 a – c if treated with organotin(IV) catalysts such as dioctyltin oxide. The reaction proceeds through transesterification of the acetoxy and alkoxy units followed by ring‐closure to form a dimeric six‐membered ring. The corresponding alkyl acetates are formed as the reaction by‐products. With these mild conditions, the method overcomes the drawbacks of previously reported synthetic routes to furnish 2,2,5,5‐tetramethyl‐1,4‐dioxa‐2,5‐disilacyclohexane ( 3 ) and even allows the synthesis of 1,4‐dioxa‐2,5‐disilacyclohexanes bearing hydrolytically labile alkoxy substituents at the silicon atom in good yields and high purity. These new materials were fully characterized by NMR spectroscopy, elemental analysis, mass spectrometry, and X‐ray analysis (trans‐ 8 a ). 相似文献
6.
Dr. Philipp Klahn Hellmuth Erhardt Dr. Andreas Kotthaus Prof. Dr. Stefan F. Kirsch 《Angewandte Chemie (International ed. in English)》2014,53(30):7913-7917
Three simple methods for the synthesis of geminal triazides are described: Starting from 1) 3‐oxocarboxylic acids, 2) iodomethyl ketones, or 3) terminal olefins, a range of triazidomethyl ketones can be constructed under mild oxidative reaction conditions by the use of IBX‐SO3K, a sulfonylated derivative of 2‐iodoxybenzoic acid (IBX), and NaN3 as an azide source. This is the first report of representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative‐scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to provide α‐azidoesters, which are potential building blocks for amino acids. 相似文献
7.
8.
W. S. Andrews E. J. Waller P. Brousseau G. Roy X. Cao K. A. M. Creber L. S. Erhardt 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(3):919-922
During the past decade, interest has increased in qualifying and quantifying the threat posed to the public by the illegal
use of radionuclides. In order to take investigations beyond the laboratory bench into more realistic scenarios, environmental
and safety considerations dictate that these studies be performed on stable and benign surrogates. This paper discusses some
of these studies, specifically the use of cerium dioxide for actinide ceramics and calcium and natural strontium ceramics
for those based on 90Sr. 相似文献
9.
10.
J. Brenneisen B. Erhardt F. Glatz Th. Kern R. Ott H. Röpke J. Schmälzlin P. Siedle B. H. Wildenthal 《Zeitschrift für Physik A Hadrons and Nuclei》1997,357(2):157-173
Assignments of I, π, T are made to 30 levels in 32S between 7.35 and 11.76 MeV excitation energy, making the spectroscopy of the T= 0 states rather complete up to 10 MeV and that of the T = 1 states up to 12 MeV. A reassessment of existing data in the light of the new results clarifies the spectrum of I π = 1+, T = 1 states up to 15 MeV excitation energy. High-spin states (I = 52 - 7) below 10 MeV excitation energy have been investigated by n t γ angular-correlation measurements with the 29Si(α, nγ) reaction at E α 14.4 MeV. Five g-wave resonances of the 31P(p, γ) reaction, leading to the formation of I π + 4+, 5+ states in 32S, have been identified between 10 and 12 MeV excitation energy. The spectrum of T = 1 states between 10.7 and 12 MeV, has been investigated by measurements of γ-ray angular distributions on resonances of the 31P(p, γ) reaction and by measurements of resonance strengths. Several 32S levels between 7.35 and 8.75 MeV excitation energy were studied as final states in resonance decays. Finally a search was performed for I π = 0+ resonances of the 28Si(α, γ) reaction. 相似文献