The title compounds were synthesized from the elements by heating the corresponding mixtures at high temperature. Their structures were determined from single-crystal X-ray diffraction. Li(9)(-)(x)()EuSn(6+)(x)(), Li(9)(-)(x)()CaSn(6+)(x)(), Li(5)Ca(7)Sn(11), and Li(6)Eu(5)Sn(9) contain columns of stacked aromatic pentagons of Sn(5)(6)(-) that are analogous to the cyclopentadienyl anion C(5)H(5)(-). The pentagons are separated with Ca(2+) or Eu(2+) in the columns and resemble a polymeric metallocene. In addition to the columns, the isostructural Li(9)(-)(x)()EuSn(6+)(x)() and Li(9)(-)(x)()CaSn(6+)(x)() contain isolated tin atoms and bent tin trimers while Li(5)Ca(7)Sn(11) and Li(6)Eu(5)Sn(9) contain flat zigzag hexamers and flat zigzag infinite chains of tin, respectively. The isostructural LiMgEu(2)Sn(3) and LiMgSr(2)Sn(3) do not contain columns of pentagons but only flat zigzag infinite chains of tin. The aromaticity of the pentagons and the conjugation of the pi-systems of the hexamers and the infinite chains are discussed. The title compounds are also characterized by magnetic and conductivity measurements. 相似文献
Continuous defect-free nanofibers containing chitosan (Ch) or quaternized chitosan (QCh) were successfully prepared by one-step electrospinning of Ch or QCh solutions mixed with poly[(L-lactide)-co-(D,L-lactide)] in common solvent. XPS revealed the surface chemical composition of the bicomponent electrospun mats. Crosslinked Ch- and QCh-containing nanofibers exhibited higher kill rates against bacteria S. aureus and E. coli than the corresponding solvent-cast films. SEM observations showed that hybrid mats were very effective in suppressing the adhesion of pathogenic bacteria S. aureus. The hybrid nanofibers are promising for wound-healing applications. 相似文献
In order to impart antibacterial properties to microfibrous electrospun materials from styrene/maleic anhydride copolymers, quaternized chitosan derivatives (QCh) containing alkyl substituents of different chain lengths are covalently attached to the mats. A complete inhibition of the growth of bacteria, S. aureus (Gram‐positive) and E. coli (Gram‐negative), for a contact time of 30–120 min or a decrease of the bacterial titer by 2–3 log units is observed depending on the quaternization degree, the chain length of the alkyl substituent, and the molar mass of QCh. The modified mats are also effective in suppressing the adhesion of pathogenic S. aureus bacteria.
The degenerate electron exchange (DEE) reaction involving radical cations (RCs) of n-nonane, n-dodecane, and n-hexadecane in n-hexane solution was studied over the temperature range 253-313 K using the method of time-resolved magnetic field effect in recombination fluorescence of spin-correlated radical ion pairs. In the dilute solutions the rate constant of DEE was found to be 200 times slower than the diffusion limit. Using n-nonane as an example, we showed that two reasons are responsible for the low value of the RC self-exchange rate: (1) conformational variability of molecules and RCs and (2) the activation barrier of DEE reaction. The calculations of the reaction enthalpy performed by the B3LYP/6-31G(d) method indicated that electron transfer can be effective only upon collision of RC with a neutral molecule either in the all-trans conformation or in the conformation differing from the latter by rotation of the end ethyl fragment. The activation barrier of the DEE reaction was estimated using the reorganization energy of the internal degrees of freedom calculated at the B3LYP level and was found to be about 6 kcal/mol. A possible influence of the interaction between RC and a neutral molecule in an encounter complex on DEE rate constant is also discussed. 相似文献
A one-dimensional singularly perturbed problem of mixed type is considered. The domain under consideration is partitioned into two subdomains. In the first subdomain a parabolic reaction-diffusion problem is given and in the second one an elliptic convection-diffusion-reaction problem. The solution is decomposed into regular and singular components. The problem is discretized using an inverse-monotone finite volume method on condensed Shishkin meshes. We establish an almost second-order global pointwise convergence in the space variable, that is uniform with respect to the perturbation parameter. 相似文献
In this paper, explicit method of constructing approximations (the triangle entropy method) is developed for nonequilibrium problems. This method enables one to treat any complicated nonlinear functionals that fit best the physics of a problem (such as, for example, rates of processes) as new independent variables.
The work of the method is demonstrated on the Boltzmann's-type kinetics. New macroscopic variables are introduced (moments of the Boltzmann collision integral, or scattering rates). They are treated as independent variables rather than as infinite moment series. This approach gives the complete account of rates of scattering processes. Transport equations for scattering rates are obtained (the second hydrodynamic chain), similar to the usual moment chain (the first hydrodynamic chain). Various examples of the closure of the first, of the second, and of the mixed hydrodynamic chains are considered for the hard sphere model. It is shown, in particular, that the complete account of scattering processes leads to a renormalization of transport coefficients.
The method gives the explicit solution for the closure problem, provides thermodynamic properties of reduced models, and can be applied to any kinetic equation with a thermodynamic Lyapunov function. 相似文献
In situ nanostructuring in bulk thermoelectric materials through thermo-dynamic phase segregation has established itself as an effective paradigm for optimizing the performance of thermoelectric materials. In bulk PbTe small compositional variations create coherent and semicoherent nanometer sized precipitates embedded in a PbTe matrix, where they can impede phonon propagation at little or no expense to the electronic properties. In this paper the nanostructuring paradigm is for the first time extended to a bulk PbS based system, which despite obvious advantages of price and abundancy, so far has been largely disregarded in thermoelectric research due to inferior room temperature thermoelectric properties relative to the pristine fellow chalcogenides, PbSe and PbTe. Herein we report on the synthesis, microstructural morphology and thermoelectric properties of two phase (PbS)(1-x)(PbTe)(x)x = 0-0.16 samples. We have found that the addition of only a few percent PbTe to PbS results in a highly nanostructured material, where PbTe precipitates are coherently and semicoherently embedded in a PbS matrix. The present (PbS)(1-x)(PbTe)(x) nanostructured samples show substantial decreases in lattice thermal conductivity relative to pristine PbS, while the electronic properties are left largely unaltered. This in turn leads to a marked increase in the thermoelectric figure of merit. This study underlines the efficiency of the nanostructuring approach and strongly supports its generality and applicability to other material systems. We demonstrate that these PbS-based materials, which are made primarily from abundant Pb and S, outperform optimally n-type doped pristine PbTe above 770 K. 相似文献