Application of NMR Spectroscopy and Imaging in Heterogeneous Biocatalysis

Heterogeneously catalyzed enzymatic glucose isomerization was considered as a model process to extend the application of nuclear magnetic resonance (NMR) and magnetic resonance imaging techniques to the studies of biocatalytic processes and heterogeneous biocatalysts. It has been demonstrated that the T ₂ times of glucose are different for its aqueous solution in the pores of an unmodified porous support and in a heterogeneous biocatalyst, comprising bacterial cells immobilized on the same support. This observation has been used to map the spatial distribution of the active component within a packed bed of biocatalyst in a model reactor. ¹³C NMR spectroscopy was applied to follow the progress of glucose isomerization catalyzed by the heterogeneous biocatalyst in a batch reactor. The utilization of proton spin decoupling and nuclear Overhauser effect was shown to be necessary to obtain high signal-to-noise ratio in the natural abundance ¹³C NMR spectra of a glucose–fructose syrup present in the packed bed of biocatalyst. The spectra thus obtained were suitable for the quantification of the glucose-to-fructose ratio achieved in the biocatalytic reaction.     

Well-Defined Oxide Core-Poly(vinyl pyrrolidone) Shell Nanoparticles: Interactions and Multi-Modal Glass Transition Dynamics at Interfaces

Interfacial interactions and dynamics were studied in silica and alumina core-poly(vinyl pyrrolidone) (PVP) shell nanoparticles with different shell thicknesses starting from 1-2 nm (monolayer); their geometry and structural organization were comprehensively characterized by several techniques. Far- and mid-IR spectroscopy, combined with DSC activation analysis of the glass transition, allowed to register hydrogen bonding and Lewis/Brønsted interactions, and the multi-modal glass transition dynamics in PVP nanoshells, as well as their interrelationship. For PVP monolayer, only a few “abnormal” modes constituted glass transition which covered the temperature range from 80 to 230 °C, with varying the activation energy by an order of magnitude.     

The Zero-Divisor Graph Associated to a Semigroup

The zero-divisor graph of a commutative semigroup with zero is the graph whose vertices are the nonzero zero-divisors of the semigroup, with two distinct vertices adjacent if the product of the corresponding elements is zero. New criteria to identify zero-divisor graphs are derived using both graph-theoretic and algebraic methods. We find the lowest bound on the number of edges necessary to guarantee a graph is a zero-divisor graph. In addition, the removal or addition of vertices to a zero-divisor graph is investigated by using equivalence relations and quotient sets. We also prove necessary and sufficient conditions for determining when regular graphs and complete graphs with more than two triangles attached are zero-divisor graphs. Lastly, we classify several graph structures that satisfy all known necessary conditions but are not zero-divisor graphs.     

Monanchoxymycalin C with anticancer properties,new analogue of crambescidin 800 from the marine sponge Monanchora pulchra

A new pentacyclic guanidine alkaloid, monanchoxymycalin C (1) was isolated from a new collection of marine sponge Monanchora pulchra along with the known monanchoxymycalin A (2). The structure of 1 was elucidated on the basis of spectroscopic data. Monanchoxymycalin C exhibits cytotoxic activity against human cancer HeLa cells at low micromolar concentrations, induces apoptosis-related death of malignant cells and inhibits cancer cell colony formation. In addition, synergistic and additive effects have been observed in combination with cisplatin.     

Enzyme‐Compatible Dynamic Nanoreactors from Electrostatically Bridged Like‐Charged Surfactants and Polyelectrolytes

Reported is an unanticipated mechanism of attractive electrostatic interactions of fully neutralized polyacrylic acid (PAA) with like‐charged surfactants. Amphiphilic polymer‐surfactant complexes with high interfacial activity and a solubilization capacity exceeding that of conventional micelles are formed by bridging with Ca²⁺ ions. Incorporation of a protease into such dynamic nanoreactors results in a synergistically enhanced cleaning performance because of the improved solubilization of poorly water‐soluble immobilized proteins. Competitive interfacial and intermolecular interactions on different time‐ and length‐scales have been resolved using colorimetric analysis, dynamic tensiometry, light scattering, and molecular dynamic simulations. The discovered bridging association mechanism suggests reengineering of surfactant/polymer/enzyme formulations of modern detergents and opens new opportunities in advancing labile delivery systems.     

Spectral,thermal and biological characterization of complexes with a Schiff base bearing triazole moiety as potential antimicrobial species

Journal of Thermal Analysis and Calorimetry - A novel series of complexes ML(ClO4)·nH2O (M: Co, Ni, Cu, Zn; HL: 2-[(E)-(1H-1,2,4-triazol-3-ylimino)methyl]phenol) have been synthesized and...     

Photophysical properties of the prefluorescent nitroxide probes QT and C343T

The photophysical properties of the nitroxide prefluorescent probes 4-(3-hydroxy-2-methyl-4-quinolinoyloxy)-2,2,6,6-tetramethyl-piperidin-4-yl) ester free radical (QT) and 2,3,4,6,7,8-hexahydro-quinolizino [1,10,9-gh] coumarin-3-carboxylic acid (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) ester free radical (C343T) were evaluated as a function of pH and solvent properties. The absorbance of QT showed high pH sensitivity. The pKa values for the different ionization forms involved in the acid-base equilibrium of the quinoline chromophore were determined in the ground and excited states. The fluorescence lifetimes of QT, and N-hydroxylamine (QTH) and quinoline methyl ester (QMe) derivatives, showed that the intramolecular quenching efficiency by the nitroxide moiety is independent of the quinoline ionization form. The fluorescence and absorbance of C343T were highly sensitive to solvent polarity in agreement with a charged transfer excited state of the chromophore. However, we noted a decrease in the intramolecular fluorescence quenching efficiency by the nitroxide moiety when changing the polarity of the solvent from hexane to water. This behavior has been attributed to a suppression of an energy transfer mechanism in the nitroxide quenching process in very polar solvents. The results obtained in micelles allow us to propose QT and C343T as sensors for pH and micropolarity, respectively, in addition to their role as monitors for free radicals or hydrogen transfer from phenols.