Chemical Composition and Antimicrobial Activity of Essential Oil from the Rhizomes of Curcuma pambrosima Growing in Vietnam

Chemistry of Natural Compounds -     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

A competitive optimization approach for data clustering and orthogonal non-negative matrix factorization

4OR - Partitioning a given data-set into subsets based on similarity among the data is called clustering. Clustering is a major task in data mining and machine learning having many applications...     

Lignin Biodegradation by a Cytochrome P450 Enzyme: A Computational Study into Syringol Activation by GcoA

A recently characterized cytochrome P450 isozyme GcoA activates lignin components through a selective O-demethylation or alternatively an acetal formation reaction. These are important reactions in biotechnology and, because lignin is readily available; it being the main component in plant cell walls. In this work we present a density functional theory study on a large active site model of GcoA to investigate syringol activation by an iron(IV)-oxo heme cation radical oxidant (Compound I) leading to hemiacetal and acetal products. Several substrate-binding positions were tested and full energy landscapes calculated. The study shows that substrate positioning determines the product distributions. Thus, with the phenol group pointing away from the heme, an O-demethylation is predicted, whereas an initial hydrogen-atom abstraction of the weak phenolic O-H group would trigger a pathway leading to ring-closure to form acetal products. Predictions on how to engineer P450 GcoA to get more selective product distributions are given.     

Second-Coordination Sphere Effects on Selectivity and Specificity of Heme and Nonheme Iron Enzymes

Mononuclear iron-containing enzymes are highly versatile oxidants that often react stereospecifically and/or regioselectively with substrates. Combined experimental and computational studies on heme monooxygenases, nonheme iron dioxygenases and halogenases have revealed the intricate details of the second-coordination sphere, which determine this specificity and selectivity. These second-coordination sphere effects originate from the positioning of the substrate and oxidant, which involve the binding of the co-factors and substrate into the active site of the protein. In addition, some enzymes affect the selectivity and reactivity through charge-stabilization from nearby bound cations/anions, an induced electric field or through the positioning of salt bridges and hydrogen-bonding interactions to first-coordination sphere iron ligands and/or the substrate. Examples of all of these second-coordination sphere effects in iron-containing enzymes and how these influence structure and reactivity are given.     

Photodegradation actuated shape-changing hydrogels

Hydrogels are attractive materials for generating 4D shapes due to their ability to undergo pronounced volume changes in response to several stimuli, including light. We previously reported shape-changing hydrogels actuated by long-wave UV and visible light in the presence of live cells using poly(ethylene glycol) macromers incorporating different photodegradable ortho-nitrobenzyl (o-NB) groups. In this comprehensive study, we determine the effect of chemical structure of different o-NB macromers (which influences molar absorptivity and rate constant of degradation), composition (macromer weight percent), fabrication design (initial gel thickness) and environment (ionic strength of solution) on light-induced hydrogel folding. We demonstrate successful photopolymerization and subsequent photodegradation of hydrogels, multistep folding, and live-cell encapsulation. This hydrogel system may be useful as new tool in stem cell differentiation and developmental biology research, facilitating the in vitro investigation of processes that are sensitive to both physical and temporal stimuli.     

The Study of the Behaviors of Zinc and Strontium in Caries-Affected Teeth by Laser-Induced Breakdown Spectroscopy(LIBS) Technique

We report on the application of Laser Induced Breakdown Spectroscopy(LIBS)technique to the study of Ca,P,Zn and Sr evolutions for adult caries-affected teeth using nanosecond laser pulses.The aim of this work is to better understand the behaviors of Zn and Sr as trace-elements in the caries eruption with respect to the behaviors of one of the main compounds of the hydroxyapatite crystal which is the calcium.The study was focused on the investigation of these elements’evolutions from three parts of the enamel surfaces of twenty two adult caries-affected teeth;the healthy part,the dental plaque part and the caries-affected part.The decrease rates of Zn,Sr and P was,also,compared to the Ca one.Comparison concerned normalized emission line intensities.For every species,normalization was done relatively to the emission line intensities of the healthy part.Results showed that abundances of these elements decrease similarly from the healthy parts to the affected-caries parts.The higher decrease rate was noticed for the calcium.The evolutions of Zn and Sr for the three parts of the teeth surfaces cannot inform about the substitution of the calcium by these trace-elements,however the comparison of their decrease rates to the calcium one can be considered as a valuable index of this substitution.