Oxidation reactions of 1,3-diphenylpropane-1,3-dione

The free radical scavenging properties and possible antioxidant activity of 1,3-diphenylpropane-1,3-dione (1) are reported. Pulse radiolysis technique was employed to study the one-electron oxidation of 1 with various radicals viz. CCl₃O₂ ^•, N₃ ^• and^•OH in homogeneous aqueous solution. All these radicals reacted with 1 under ambient conditions at almost diffusion controlled rates producing transient species with an absorption maximum around 420 nm that decayed at first order rates. The transient absorption peak was shifted in the case of CCl₃OO^• radical reaction with 1 due to change in the polarity of the medium. Formation of a stable product with a broad absorption band starting from 400 nm and cut off at 230 nm was observed in the oxidation of 1 with^•OH and^•N₃ radicals. In a biological system also, 1 showed significant inhibitory activity against Fe²⁺-mediatedlipidperoxidation. Based on these observations, a suitable mechanism for the oxidation of 1 has been proposed.     

Characterization of forcibly k-variegated degree sequences,k⩾3

We characterize forcibly k-variegated degree sequences for k?3.     

Note on Choudum's “chromatic bounds for a class of graphs”

If a graph G has no induced subgraph isomorphic to K_1,3′ K₅-e, or a third graph that can be selected from two specific graphs, then the chromatic number of G is either d or d + 1, where d is the maximum order of a clique in G.     

White matter hyperintensities and dynamics of postural control

Background

White matter hyperintensities (WMHs) on MRI have been associated with age, cardiovascular risk factors and falls in the elderly. This study evaluated the relationship between WMHs and dynamics of postural control in older adults without history of falls.

Methods

We studied 76 community-living subjects without history of falls (age 64.5±7.3 years). Brain and WMH volume calculations and clinical rating were done on fluid-attenuation inversion recovery (FLAIR) and MP-RAGE MR images on 3 T. Balance was assessed from the center of pressure displacement using the force platform during 3 min of quiet standing using traditional and dynamic measures (using stabilogram-diffusion analysis). Gait speed was measured from 12-min walk.

Results

Age-adjusted periventricular and focal WMHs were associated with changes in certain dynamic balance measures, including reduced range of postural sway in anteroposterior direction (fronto-temporal WMHs, P=.045; parieto-occipital WMHs, P=.009) and more irregular long-term mediolateral fluctuations (P=.046). Normal walking speed was not affected by WMHs.

Conclusions

Periventricular and focal WMHs affect long-term dynamics of postural control, which requires engagement of feedback mechanisms, and may contribute to mobility decline in the elderly.     

Versatile synthesis and mechanism of activation of S-benzoxazolyl glycosides

As a part of a program for developing new efficient procedures for stereoselective glycosylation, a range of S-benzoxazolyl (SBox) glycosides have been synthesized. The mechanistic aspects of the SBox moiety activation for glycosylation via a variety of conceptually different pathways in the presence of thiophilic, electrophilic, or metal-based promoters have been investigated.     

Photophysical characteristics and density functional theory calculations of indole 2-carboxylic acid in the presence of mercurous ions

Many photo-physical studies have been reported for the detection of Hg²⁺ ions. Here we present the effect of Hg ₂ ²⁺ ions on the absorption and fluorescence of indole-2-carboxylic acid (I2C). Experimental evidence, supported by density functional theory B3LYP/LANL2DZ/PCM, for the formation of a I2C-Hg ₂ ²⁺ complex, is reported for the first time. It was observed that I2C forms a ground-state complex with Hg ₂ ²⁺ ions in a ratio of 3:1. The possibility of I2C to be used as a selective novel chemical sensor for the spectrophotometric detection of mercurous ions is described.     

Application of glycosyl thioimidates in solid-phase oligosaccharide synthesis

Two stable classes of thioimidoyl derivatives, S-benzoxazolyl (SBox) and S-thiazolinyl (STaz) glycosides, were investigated as glycosyl donors for solid-phase oligosaccharide synthesis. It was demonstrated that these derivatives are suitable for both glycosyl acceptor-bound and glycosyl donor-bound strategies, commonly employed in resin-supported oligosaccharide synthesis.     

Studies on heterocyclic polyurea–epoxy resin condensation products

Polyureas having different heterocyclic groups were reacted, respectively, with commercial epoxy resins, i.e., diglicidyle ether of bisphenol A and brominated DGEBA. The resultant polyurea–epoxy systems were designated as I_(a–f) and II_(a–f), respectively. All the polyurea–epoxy systems were characterized by FTIR spectral studies, thermogravimetric analysis and number average molecular weight, estimated by non-aqueous conductometric titration. The polyurea–epoxy systems were then mixed with appropriate amounts of DGEBA epoxy resin, monitored for differential scanning calorimetry, and, based on this, glass fiber-reinforced composites were prepared. All the resultant laminates were characterized by physical and mechanical properties.     

Different Conformation of Thiol Protease Inhibitor During Amyloid Formation: Inhibition by Curcumin and Quercetin

Cystatins are thiol proteinase inhibitors ubiquitously present in mammalian body and serve various important physiological functions. In the present study, we examined the effects of acid denaturation on newly identified thiol protease inhibitors from the lungs of Capra hircus (Goat) with a focus on protein conformational changes and amyloid fibril formation. Acid denaturation as studied by CD (Circular Dichroism) and fluorescence spectroscopy showed that purified inhibitor named GLC (Goat Lung Cystatin) populates three partly unfolded species, a native like state at pH?3.0, a partly unfolded intermediate at pH2.0, and unstructured unfolded state at pH?1.0, from each of which amyloid like fibrils grow as assessed by thioflavin T (ThT) spectroscopy. The result showed, native like structure formed at pH?3.0 is more responsive towards amyloid formation when compare to other conformation of proteins. Morphology of the protein species incubated for amyloid process was observed using transmission electron microscopy (TEM). Moreover, anti-fibrillogenic effects of curcumin and quercetin were analysed using ThT binding assay. Curcumin and quercetin produced a concentration dependent decline inThT fluorescence suggesting deaggregation of the fibrils. When added prior to amyloid fibril initiation 50 μM curcumin inhibited amyloid aggregation. However, more quercetin is needed to prevent the same extent of fibrillation. Implications for therapeutics in view of polyphenols as essential nutrients are suggested in lung diseases.