Core-shell structured electrode materials for lithium ion batteries

Recent progress in studies of several types of core-shell structured electrode materials, including TiO₂/C, Si/C, Si/SiO _x , LiCoO₂/C, and LiFePO₄/C nanocomposites, including details of their preparation and their electrochemical performance is briefly reviewed. Results clearly show that the coating shell can effectively prevent the aggregation of the nanosized cores, which are the electrochemically active materials. In addition, the diffusion coefficients of lithium ions can be increased, and the reversibility of lithium intercalation and deintercalation is improved. As a result, the cycling behavior is greatly improved. The reviewed results suggest that core-shell nanocomposites are a good starting point for further development of new promising electrode materials.

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Modeling of solvent viscosity effects on the electroreduction of Pt(II) aquachlorocomplexes

Solvent dynamics effects on the electroreduction of [PtCl₃(H₂O)]⁻ at a mercury electrode are explored in the framework of Sumi–Marcus model using an efficient computational scheme. According to results of density functional calculations, the second electron transfer step may be regarded as rate controlling. The nonmonotonous influence of solvent viscosity on the reaction rate is predicted and explained in terms of the saddle point avoidance. The results of model calculations are employed to interpret experimental data reported earlier in the literature.

A comparative study of hydrothermal and sol–gel methods in the synthesis of MnO<Subscript>2</Subscript> nanostructures

In this work, MnO₂ nanostructure powders with different crystalline phases have been successfully prepared by hydrothermal and sol–gel methods. The obtained products were characterized by XRD and SEM techniques and their crystallographic phases and morphological properties compared. Results showed that α-MnO₂, β-MnO₂, and δ-MnO₂ nanorods were synthesized by hydrothermal method and γ-MnO₂ polymorph was obtained by sol–gel method.

Synthesis and dopamine receptor binding affinity of 4H-thiochromenoapomorphines

Abstract  The synthesis of 4H-thiochromene derivatives of apomorphines, a novel class of isoquinoline alkaloid-related compounds, has been achieved by different O-dealkylation methods applied on previously published heteroring-fused aporphinoids. Detailed DFT study has been presented regarding the mechanism of the L-selectride-mediated multiple O-dealkylation of a seven-ring aporphine analogue. Dopamine-binding tests confirmed the essential function of 11-hydroxy moiety of the aporphine skeleton and revealed a remarkable D₁ over D₂ specificity for the derivative having the 4H-thiochromene ring system attached to positions 2 and 3 of the aporphine backbone. Graphical Abstract  

Synthesis and crystal structures of two polymorphs of sulfathiazole:pyridine (1:1) adducts

The paper summarizes recent results on crystallization and characterization of two polymorphs of the sulfathiazole:pyridine (1:1) adducts with substantially different space groups (P4₁ and P2₁/c) and packing. Intermolecular interactions in the adducts are compared. These two forms were obtained from solutions containing different ratios of n-propanol, not participating directly in crystallization but obviously controlling the polymorphism, and pyridine. The adducts are also formed by the contact of pure solid sulfathiazole (different polymorphs) with pyridine vapor. In air, the adducts decompose giving initially the metastable polymorph I of sulfathiazole, and then the stable sulfathiazole-III.

Three crystal structures reported as lacking centers that should be refined as centrosymmetric

The compounds {[Fe(phen)₃]²⁺(TCNQ–TCNQ)²⁻) · 2(CH₃OH)} (FIWPRD), {[Fe(C₅H₅)(C₅H₄CH₂NMe₃)]⁺)(TCNQ⁻) (IKONOL), and {[Cu(1,4,5,12-tetraazacyclo-pentadecane)]²⁺(TCNQ⁻)₂} (AVOJEA) were reported in the non-centrosymmetric space groups Cc (#9), Pna2₁ (#33), and P1 (#1). Examination of the several sets of atomic coordinates shows that the space groups are more likely to be C2/c (#15), Pnma (#63), and (#2), respectively. Confirmation of the centrosymmetric models requires access to the diffraction intensities; unfortunately these are not in the public domain.

NMR and HPLC study of chiral selectors with naphthyl unit

Doubling of resonances in NMR spectra of chiral selectors with naphthyl group attached to the tertiary amide nitrogen atom has been noticed what revealed the presence of two isomers. To test the enantiorecognition ability of these chiral selectors they are covalently bonded to the HPLC silica gel. Those kind of chiral stationary phases were compared with analogous commercial leucine chiral stationary phase. They exhibit the better enantioseparation results which indicate that the existence of cis/trans isomers does not have the negative influence on their enantioselective ability.

A fluorous tag-bound fluorescence derivatization reagent, F-trap pyrene, for reagent peak-free HPLC analysis of aliphatic amines

We have developed a novel pre-column fluorescence derivatization reagent for amines, F-trap pyrene. This reagent comprises a fluorescent pyrene moiety, an amine-reactive Marshall linker, and a fluorophilic perfluoroalkyl group known as fluorous tag. When the reagent reacts with aliphatic amines and amino acids to give fluorescent derivatives, the fluorous tag in the reagent is eliminated simultaneously. Therefore, excess unreacted reagents in the derivatization reaction solution still have the fluorous tag and could be removed by fluorous solid-phase extraction selectively before high-performance liquid chromatography (HPLC) analysis. By using this reagent, 13 kinds of aliphatic amine (C₂–C₁₆) derivatives can be separated within 40 min by reversed-phase HPLC with gradient elution. In this chromatogram, unreacted reagents peak at around 28 min, greatly decrease after fluorous solid-phase extraction, and do not interfere with the quantification of each amine. The detection limits (S/N = 3) for examined aliphatic amines are 3.6–25 fmol per 20 μL injection. We have also applied this reagent successfully to the amino acid analysis.

X-ray structural analyses and DFT study of 7-thianorbornenes: 4-aza-4-phenyl-10-thiatricyclo[5.2.1.0.<Superscript>2,6</Superscript>]deca-8-ene-3,5-dione and 4-aza-l,4,7-trimethyl-10-thiatricyclo[5.2.1.0.<Superscript>2,6</Superscript>]deca-8-ene-3,5-dione

X-ray structures of Diels–Alder adducts of thiophene with N-methylmaleimide and 2,5-dimethylthiophene with N-phenylmaleimide were determined and compared to literature data. In addition, quantum chemical calculations at various levels of theory were used to study their molecular and electronic structure. A comparison with experimental results showed that MP2/6-31G^*, HF/6-311+G^** and PBE1PBE/6-31G^* methods give the most accurate structures.

Small bite angle diphosphines: synthesis of Ph(p-tolyl)PCH2PPh(p-tolyl) upon lithium reduction of Ph2P(p-tolyl)—molecular structure of anti-[Mo(CO)4{Ph(p-tolyl)PCH2PPh(p-tolyl)}]

Lithiation of Ph₂P(p-tolyl) followed by quenching with dichloromethane affords the new diphosphine Ph(p-tolyl)PCH₂PPh(p-tolyl) as a mixture of syn and anti isomers. Upon crystallisation the anti isomer can be isolated relatively pure and reaction of this with [Mo(CO)₄(piperidine)₂] gives anti-[Mo(CO)₄{Ph(p-tolyl)PCH₂PPh(p-tolyl)}] which has been crystallographically characterised. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Properties of the electronic density of states in TiO<Subscript>2</Subscript> nanoparticles surrounded with aqueous electrolyte

Results on the density of sates of nanostructured TiO₂ as a function of particle size and temperature are reported. In TiO₂ nanoparticles with a mean diameter 10 nm, the density of states (DOS) is strongly temperature-dependent, indicating a rearrangement of the bandgap states in which the exponential energy parameter (width of the distribution) increases from 0.080 to 50 °C. For nanoparticles with mean diameters of 20 and 30 nm the DOS is much closer to an exponential distribution, and is much less sensitive to temperature variations. It is suggested that nanometer confinement has a significant influence on the density of electronic states for 10-nm particles, while band tailing is similar to that occurring in bulk semiconductors for the larger particles.

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Kinetics of substitution at [tris(3,5-dimethylpyrazolyl)-hydroborato]molybdenum nitrosyl dihalides by alcohols and by aniline

The kinetics of substitution by alcohols and by aniline at [tris(3,5-dimethylpyrazolyl)hydroborato]molybdenum nitrosyl dihalides in toluene solution at 298.2 K and at atmospheric pressure are reported and interpreted in terms of an associative mechanism.

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Chemistry,commentary and community: Discussion of “The NaDyBr<Subscript>4</Subscript> complex: its molecular structure and thermodynamic properties” by Varga and Hargittai

The molecular geometries, relative stabilities, binding energies, and dissociation energies of NaDyBr₄ and its molecular ion are discussed. Both the bidentate and tridentate isomers are stable for the neutral species, while only the bidentate form is stable for NaDyBr₄ ⁺.

Self-assembling process of zirconium oxide suspension induced by vaporization of volatile solvents

We investigated the self-assembling processes of solutions of poly(vinyl methyl ether) in mixed solvents of 2-butanone and water with and without zirconium oxide (ZrO₂) particles with average size of 75 nm during vaporization of the solvents by means of optical microscopy. The self-assembling processes can be classified into three regimes: (1) early stage (nucleation and growth regime), (2) intermediate stage (regularly arranged regime), and (3) late stage (aggregation and coalescence regime). In the intermediate stage, the water droplets, including the ZrO₂ particles, were regularly arranged with an almost constant spacing. The mechanism of the self-assembling processes is discussed on the basis of experimental results.

Branched trichain sulfosuccinates as novel water in CO2 dispersants

A series of highly branched trichain sulfosuccinate surfactants have been synthesized and studied in condensed CO₂ and aqueous environments. Aqueous critical micelle concentrations (CMCs) showed a general trend of increasing CMC with decreasing chain length, whereas increased branching appeared to increase solubility in CO₂ and aid the dispersion of water. Near infrared spectra confirmed observed cloud with a large increase in solubility above the cloud pressures in this solvent.

The magnetic concentration gradient force—Is it real?

There are suggestions in the electrochemical literature that a body force F _∇c acts when an electrolyte with a non-uniform concentration c of paramagnetic ions is subject to a uniform magnetic field. We demonstrate, experimentally and theoretically, that no such magnetic body force exists, to first order. A second-order correction associated with the demagnetizing field does lead to a very small concentration-dependent body force, which is not expected to produce any observable effect in electrochemistry. Contribution to special issue on Magnetic field effects in Electrochemistry.

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Electrochemistry and catalytic behavior of immobilized binuclear complexes of copper(II) and nickel(II) with Robson type ligand

Various systems containing immobilized binuclear copper(II) and nickel(II) complexes with Robson type ligand ([M₂L]Cl₂) are studied and compared in relation to catalysis of hydrogen peroxide reduction. Molecular complexes adsorbed on mercury and gold, crystalline complexes immobilized in the carbon paste electrode, and complex species entrapped into polyphenol-modified gold electrodes are considered. Electrocatalysis is assumed to result from the formation of H₂O₂–[M₂L]Cl₂ adduct, not from mediating redox transformations. Possible geometry of the formed reaction layers supporting adduct formation is discussed.

NEMCA effect: why are the work function changes of the gas exposed catalyst-electrode surface one-to-one related to the changes in the catalyst working electrode potential?

In the present work, an important point concerning the NEMCA effect is addressed. We analyse the reasons why the changes in the work function of the gas exposed catalyst-electrode surface are one to one related to the changes in the catalyst working electrode potential E with respect to a reference electrode. It is concluded that this is due to the unique properties of the catalyst/solid electrolyte interface: the structure of the double layer in this region is very different from that in liquid electrolytes, being the potential difference at this interface mainly determined by the specific adsorption of the mobile species in the solid electrolyte.

A note on Michael Weisberg’s: challenges to the structural conception of chemical bonding

Michael Weisberg’s recent 2007 paper on the chemical bond makes the claim that the chemical notion of the covalent bond is in trouble. This note casts doubts on that claim.

A novel Ce<Superscript>III</Superscript>-cyclam type complex and its redox chemistry in aqueous solutions

A new Ce^III complex was synthesized by mixing the ligand “dioxocyclam” with Ce^III ions at pH 8.0 and its redox properties were investigated.