Electrochemical and structural study of LiCoPO<Subscript>4</Subscript>-based electrodes

LiCoPO₄ samples were synthesized by two different techniques (high-temperature solid-state reaction and lower-temperature synthesis using NH₄CoPO₄·H₂O as precursor) and tested as cathode materials for 5-V lithium batteries. An irreversible lithium deinsertion was observed for the high-temperature sample. In contrast, the application of lower-temperature synthesis led to a significant improvement of the lithium storage reversibility. Different delithiation mechanisms in LiCoPO₄ were found for the samples obtained by different synthetic techniques. The nature of capacity fading during cycling of the cells is discussed.     

Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations

The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well.     

Palladium(I) carbonyl carboxylate clusters cyclo-[Pd2(μ-CO)2(μ-OCOR)2]n (n = 2 or 3): Structure and reactivity

The interaction of palladium(+1) cluster Pd₄(μ-CO)₄(μ-OAc)₄ with saturated and unsaturated carboxylic acids was studied. It was found, that the substitution of acetates groups on others carboxylates leads to the clusters with different nuclearity. Palladium(+1) carbonyl carboxylate complexes of composition [Pd(μ-CO)(μ-OCOR)]_n, where R = CF₃, CCl₃, CH₂Cl, MeCH = CMe, Me, Prⁱ, Bu, Buⁱ, Bu^tert, n-C₅H₁₁ and n = 4 or 6 were synthesized. According to X-ray data all clusters possess cyclic planar metal cores with alternate pairs of μ-carbonyl and μ-carboxylate ligands. The presence of bulky alkyl fragments in the carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(+1) carbonyl acetate of composition Pd₄(μ-CO)₄(μ-OAc)₄ due, apparently, to steric hindrance.     

Polyelectrolyte-mediated protein adsorption: fluorescent protein binding to individual polyelectrolyte nanospheres

We have used confocal fluorescence microscopy with single molecule sensitivity to characterize uptake and release of fluorescent protein (mEosFP) molecules by individual spherical polyelectrolyte brush (SPB) nanoparticles that were immobilized on a glass surface. The SPB particles consisted of a solid core particle of 100 nm diameter onto which long polyelectrolyte chains were affixed. They could be loaded with up to 30 000 mEosFP molecules in a solvent of low ionic strength. The concentration dependence of protein loading can be described with a simple bimolecular binding model, characterized by an equilibrium dissociation coefficient of 0.5 microM. Essentially complete release of the bound proteins was observed after increasing the ionic strength by adding 250 mM NaCl to the solvent. Fluorescence emission spectra and time-resolved fluorescence intensity decays were measured on individual, mEosFP-loaded SPB nanoparticles, and also on the dissolved mEosFP before and after adsorption. These results indicate that the mEosFP molecules remained structurally intact in this procedure. Hence, the present investigation demonstrates unambiguously that polyelectrolyte-mediated protein adsorption onto SPB particles presents a viable process for protein immobilization.     

Gold nanoparticle patterning of silicon wafers using chemical e-beam lithography

This paper demonstrates a novel facile method for fabrication of patterned arrays of gold nanoparticles on Si/SiO2 by combining electron beam lithography and self-assembly techniques. Our strategy is to use direct-write electron beam patterning to convert nitro functionality in self-assembled monolayers of 3-(4-nitrophenoxy)-propyltrimethoxysilane to amino functionality, forming chemically well-defined surface architectures on the 100 nm scale. These nanopatterns are employed to guide the assembly of citrate-passivated gold nanoparticles according to their different affinities for amino and nitro groups. This kind of nanoparticle assembly offers an attractive new option for nanoparticle patterning a silicon surface, as relevant, for example, to biosensors, electronics, and optical devices.     

Diastereoselective synthesis of (2S)-2-[(R)-1H-indol-3-yl(phenyl)methyl]-2,3-dihydro-1H-inden-1-one

Double asymmetric induction in Michael reactions has been studied. Enantioselective alkylation of a cyclic ketone (1-indanone) with α-phenyl-nor-gramine was carried out. The relative configuration of (2S^∗)-2-[(R^∗)-1H-indol-3-yl(phenyl)methyl]-2,3-dihydro-1H-inden-1-one was established by X-ray diffraction. The relative configuration of (R^∗,R^∗,S^∗)- and (S^∗,R^∗,S^∗)-2-1H-indol-3-yl(phenyl)methyl]-2,3-dihydro-1H-inden-1-ols was established by ¹H NMR studies.     

Effect of polymer charge density and ionic strength on the formation of complexes between sodium arylamido-2-methyl-1-propane-sulfonate-co-acrylamide gels and cetylpyridinium chloride

The effects of sodium chloride on the composition and structure of polyelectrolyte gel-surfactant complexes (PSCs) formed by the sodium salt of acrylamide-2-methyl-1-propane-sulfonic acid-co-acrylamide gels and cetylpyridinium chloride have been studied. At a low ionic strength of the solution, the composition of all the complexes is close to stoichiometric by charge. In the presence of 0.3 M sodium chloride, the composition of the complexes formed by the gel with 99 mol % charged groups is close to stoichiometric, while for the gel with 33 mol % charged monomer units, a nonstoichiometric complex with a high excess of the surfactant is formed. Further decrease of the charge density up to 10 mol % leads to partial or complete dissociation of the PSCs. The study of PSCs by the method of small-angle X-ray scattering (SAXS) shows that the complexes formed by the gels with high and intermediate charge densities are highly ordered. The decrease of the charge density of the swollen networks at first leads to a change in symmetry of the ordered domains in the PSCs and then to their disordering. The formation of nonstoichiometric PSCs at a high enough concentration of salt is explained by the effect of fitting, when the packing of the surfactant and polymer components in the PSCs is improved due to the inclusion of extra surfactant molecules together with their counterions in the ordered domains.     

On copositive approximation by algebraic polynomials

Для функцииf ∈C[?1, 1] с ог раниченным числом пе ремен знака строится последовательность многочленовр _п , коположительных сf (т.е.f(x)p _n (x)≥0, ?1≤х<1) и таких, что $$\left\| {f - p_n } \right\|_\infty \leqslant C\omega _\varphi ^3 (f,n^{ - 1} ),$$ гдеω _? ³ (f, δ) — модуль непр ерывности Дитциана-Т отика третьего порядка. Изв естно, чтоω _? ³ нельзя заменить ни наω _? ⁴ , ни на ω⁴. Таким образом, приведенная оценка точна в некотором смы сле. В качестве следст вия установлена эквивал ентность соотношений $$E_n (f) = O(n^{ - \alpha } )\user2{}E_n^{(0)} (f,r) = O(n^{ - \alpha } )\user2{}0< \alpha< 3.$$