Voltammetric studies of microcrystalline C60 adhered to a carbon electrode surface and placed in contact with aqueous electrolyte containing potassium ions

The reduction of microcrystalline C₆₀ fullerene, adhered at a carbon electrode and immersed in aqueous electrolyte, has been studied under various voltammetric conditions. This work reports mainly the voltammetric studies carried out principally in electrolyte containing potassium ions. Comparison of adherence techniques, such as solvent casting and mechanical transfer methods, are made to assess if the type of adhered techniques has any significant influence on the observed electrochemistry. The solvent casting method is found to produce three peaks in the potential for C₆₀^0/n- redox couple as compared to a single and large peak produced when a mechanical transfer technique is employed. When the reduction potential of microcrystalline C₆₀ in the presence of K⁺ is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C₆₀^0/n- redox couple during cyclic voltammetry is observed to change with concentration of the cations and the observed electrochemistry can be attributed to a cation-exchange mechanism. The reduction of C₆₀ is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K _n C₆₀ fulleride, which does not appear to undergo dissolution is obtained under cyclic voltametric conditions. This coating remains electrochemically active in the presence of tetrabutylammonium ions in acetonitrile. Scan rate, chronocoulometric, and scanning electron microscopic studies provide evidence of the presence of a surface process involving solid–solid transformation.     

Effect of electron donor-acceptor interaction on the thermal stability of supramolecular side chain liquid crystalline polymers based on poly(3-carboxypropylmethylsiloxane)

Supramolecular side chain liquid crystalline polymers were prepared from poly(3-carboxypropylmethylsiloxane) (PSI100) and azobenzene-based derivatives through intermolecular hydrogen bonding between the carboxylic acid groups of PSI100 and the imidazole rings in the azobenzene-based derivatives. The presence of H-bonding was confirmed using FTIR spectroscopy. The polymeric complexes behave as liquid crystalline polymers and exhibit nematic mesophases identified on the basis of the observation of Schlieren textures. The mesogenic behaviour of these complexes was studied by polarizing optical microscopy and X-ray diffraction. The thermal behaviour of the complexes was investigated by differential scanning calorimetry. On increasing the spacer length, the transition temperatures initially increase. A further increase in spacer length, however, leads to a decrease in the transition temperatures. The electron donor-acceptor interaction between unlike mesogenic units in supramolecular copolymeric complexes helps to stabilize the mesophase.     

Improving Resolution of Isomeric Flavonoids and Their Glycosides Using Two-Dimensional Liquid Chromatography Coupled With High-Resolution Mass Spectrometry

Chromatographia - The separation of isomers is one of the key issues in analysing complex natural matrices, thus commanding a higher separating power from the applied analytical system. In this...     

Polymerization behavior of 2,2,6,6-tetramethylpiperidinyl methacrylate: A monomer carrying a hindered amine group

Copolymers of 2,2,6,6-tetramethylpiperidinyl methacrylate (TPMA) with styrene (S) and with methyl methacrylate (MMA) were synthesized using AIBN as initiator. S–TPMA copolymers from feed ranging from 0.10–0.80 mole fractions TPMA and MMA-TPMA copolymers from feed of 0.04–0.85 mole fractions TPMA were used in the determination of monomer reactivity ratios r₁, r₂. Four different methods were employed in the calculations of r₁ and r₂ and all calculated results were in good agreement with each other. The structure of S–TPMA copolymers was inferred to be of an alternating nature while that of MMA–TPMA copolymers was random. Both copolymers are potential hindered amine light stabilizers (HALS) and are expected to be less extractable from, and more compatible with, polystyrene and poly(methyl methacrylate) base polymers.     

Band-limited refinable functions for wavelets and framelets

Extending band-limited constructions of orthonormal refinable functions, a special class of periodic functions is used to generate a family of band-limited refinable functions. Characterizations of Riesz bases and frames formed by integer shifts of these refinable functions are obtained. Such families of refinable functions are employed to construct band-limited biorthogonal wavelet bases and biframes with desirable time-frequency localization.     

Preparation of Papers

We motivate the study of a vector variational inequality by a practical flow equilibrium problem on a network, namely a generalization of the well-known Wardrop equilibrium principle. Both weak and strong forms of the vector variational inequality are discussed and their relationships to a vector optimization problem are established under various convexity assumptions.     

Algorithms for Unconstrained Optimization Problems via Control Theory

Existing algorithms for solving unconstrained optimization problems are generally only optimal in the short term. It is desirable to have algorithms which are long-term optimal. To achieve this, the problem of computing the minimum point of an unconstrained function is formulated as a sequence of optimal control problems. Some qualitative results are obtained from the optimal control analysis. These qualitative results are then used to construct a theoretical iterative method and a new continuous-time method for computing the minimum point of a nonlinear unconstrained function. New iterative algorithms which approximate the theoretical iterative method and the proposed continuous-time method are then established. For convergence analysis, it is useful to note that the numerical solution of an unconstrained optimization problem is none other than an inverse Lyapunov function problem. Convergence conditions for the proposed continuous-time method and iterative algorithms are established by using the Lyapunov function theorem.     

A stochastic model for risk management in global supply chain networks

With the increasing emphasis on supply chain vulnerabilities, effective mathematical tools for analyzing and understanding appropriate supply chain risk management are now attracting much attention. This paper presents a stochastic model of the multi-stage global supply chain network problem, incorporating a set of related risks, namely, supply, demand, exchange, and disruption. We provide a new solution methodology using the Moreau–Yosida regularization, and design an algorithm for treating the multi-stage global supply chain network problem with profit maximization and risk minimization objectives.