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181.
TMSOTf-promoted glycosylations of 2-azido-2-deoxy-glucosyl trichloroacetimidates provide excellent alpha-anomeric selectivities when performed at a relatively high reaction temperature in the presence of PhSEt or thiophene. NMR and computation studies have shown that these glycosylations proceed through an equatorial anomeric sulfonium ion, which upon displacement by a sugar alcohol provides an axial glycoside. Computational studies have indicated that steric factors determine the selective formation of the beta-anomeric sulfonium ion. 相似文献
182.
Dr. Nikita V. Chukanov Prof. Roman V. Shchepin Dr. Sameer M. Joshi Mohammad S. H. Kabir Dr. Oleg G. Salnikov Alexandra Svyatova Prof. Igor V. Koptyug Prof. Juri G. Gelovani Prof. Eduard Y. Chekmenev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9727-9736
NMR hyperpolarization techniques enhance nuclear spin polarization by several orders of magnitude resulting in corresponding sensitivity gains. This enormous sensitivity gain enables new applications ranging from studies of small molecules by using high-resolution NMR spectroscopy to real-time metabolic imaging in vivo. Several hyperpolarization techniques exist for hyperpolarization of a large repertoire of nuclear spins, although the 13C and 15N sites of biocompatible agents are the key targets due to their widespread use in biochemical pathways. Moreover, their long T1 allows hyperpolarized states to be retained for up to tens of minutes. Signal amplification by reversible exchange (SABRE) is a low-cost and ultrafast hyperpolarization technique that has been shown to be versatile for the hyperpolarization of 15N nuclei. Although large sensitivity gains are enabled by hyperpolarization, 15N natural abundance is only ∼0.4 %, so isotopic labeling of the molecules to be hyperpolarized is required in order to take full advantage of the hyperpolarized state. Herein, we describe selected advances in the preparation of 15N-labeled compounds with the primary emphasis on using these compounds for SABRE polarization in microtesla magnetic fields through spontaneous polarization transfer from parahydrogen. Also, these principles can certainly be applied for hyperpolarization of these emerging contrast agents using dynamic nuclear polarization and other techniques. 相似文献
183.
For arbitrary values of n and l quantum numbers, we present a simple exact analytical solution of the D-dimensional (D ≥ 2) hyperradial Schr?dinger equation with the Kratzer and the modified Kratzer potentials within the framework of the exact
quantization rule (EQR) method. The exact bound state energy eigenvalues (E
nl
) are easily calculated from this EQR method. The corresponding normalized hyperradial wave functions (ψ
nl
(r)) are also calculated. The exact energy eigenvalues for these Kratzer-type potentials are calculated numerically for a few
typical LiH, CH, HCl, CO, NO, O2, N2 and I2 diatomic molecules for various values of n and l quantum numbers. Numerical tests using the energy calculations for the inter dimensional degeneracy (D = 2 − 4) for I2, LiH, HCl, O2, NO and CO are also given. Our results obtained by EQR are in exact agreement with those obtained by other methods. 相似文献
184.
This article studies the robustness of confidence interval construction for the intraclass kappa statistic based on a dichotomous response when the assumption of marginal homogeneity across two raters is violated. Two methods of construction are considered: the goodness-of-fit approach and the modified Wald method. Evaluation was done by exact calculation of the confidence interval coverage produced by these approaches. It was found that under mild departures from marginal homogeneity (differences in rater success rates of $<$ 10 %), the goodness- of-fit approach can be recommended. Moreover, under these same conditions, Cohen’s kappa tends to be less biased as a point estimator than the intraclass kappa statistic. 相似文献
185.
As a natural outgrowth of the work done in Chavan (Proc Edin Math Soc 50:637–652, 2007; Studia Math 203:129–162, 2011), we introduce an abstract framework to study generating m-tuples, and use it to analyze hypercontractivity and hyperexpansivity in several variables. These two notions encompass (joint) hyponormality and subnormality, as well as toral and spherical isometric-ness; for instance, the Drury–Arveson 2-shift is a spherical complete hyperexpansion. Our approach produces a unified theory that simultaneously covers toral and spherical hypercontractions (and hyperexpansions). As a byproduct, we arrive at a dilation theory for completely hypercontractive and completely hyperexpansive generating tuples. We can then analyze in detail the Cauchy duals of toral and spherical 2-hyperexpansive tuples. We also discuss various applications to the theory of hypercontractive and hyperexpansive tuples. 相似文献
186.
We obtain the exact energy spectra and corresponding wave functions of the spherical quantum dots for any (n,l) state in the presence of a combination of pseudo-harmonic, Coulomb and linear confining potential terms within the exact analytical iteration method (EAIM). The interaction potential model under consideration is labeled as the Cornell modified-plus-harmonic (CMpH) type which is a correction form to the harmonic, Coulomb and linear confining potential terms. 相似文献
187.
Summary Thiols are reacted at pH 7 with an excess of ferricyanide. The excess of reagent is determined by adding a measured excess of ascorbic acid followed by back titration of ascorbic acid with 2,6-dichlorophenolindophenol. A correction can be made for ascorbic acid, if present with thiols. Tested with dilute solutions of cysteine, glutathione, mercaptoacetic acid and some other water-soluble thiols gave results which are accurate to 0.1%. Glycine, cystine, methionine, etc. do not interfere.
Zusammenfassung Thiole reagieren bei pH 7 mit überschüssigem Cyanoferrat (III). Der Überschuß läßt sich durch Zusatz einer gemessenen Menge Ascorbinsäure und deren Rücktitration mit 2,6-Dichlorphenolindophenol bestimmen. Ist neben Thiol bereits Ascorbinsäure zugegen, so ist eine entsprechende Korrektur anzubringen. Die Anwendung auf Lösungen von Cystein, Glutathion, Mercaptoessigsäure und einigen anderen wasserlöslichen Thiolen erbrachte auf 0,1% genaue Ergebnisse. Glycin, Cystin, Methionin usw. stören nicht.相似文献
188.
189.
The research described in this paper primarily involves mesoscale simulations: dissipative particle dynamics (DPD) of packed assemblies of oriented fibers suspended in a viscous medium. Computer simulations have been performed in order to explore how the aspect ratio and degree of fiber alignment affect the critical volume fraction (percolation threshold) required to achieve electrical conductivity. The fiber network impedance was assessed using Monte Carlo simulations after establishing the structural arrangement with DPD. The predictions are compared with the predictions of classical percolation theory and found to be in close agreement. The approach is thus validated and can be extended to systems that cannot be tackled analytically; in particular, the work is motivated by long-standing interest in materials which display a complex percolation behavior. 相似文献
190.
Scope and limitations of Pd2(dba)3/P(i-BuNCH2CH2)3N-catalyzed Buchwald-Hartwig amination reactions of aryl chlorides 总被引:2,自引:0,他引:2
Proazaphosphatrane ligands in combination with Pd(2)(dba)(3) generate highly active catalysts for Buchwald-Hartwig amination of aryl chlorides. In particular, commercially available P(i-BuNCH(2)CH(2))(3)N is a highly general and efficient ligand, allowing the coupling of an electronically diverse set of aryl chlorides, including chloropyridines, with a wide variety of amines using 1 mol % of Pd at 100 degrees C. Either a 1:1 or 2:1 ratio of ligand to Pd was found to be effective. This catalyst system performs exceptionally well for sterically hindered substrates, even with only 0.25 mol % of Pd. It is shown that NaOH can also be used as the base (instead of NaO-t-Bu) allowing functionalized substrates to participate in these reactions. 相似文献