Radiation chemistry of tris(acetylacetonato) cobalt(iii) in aqueous solutions

Abstract

On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C₂H₂OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 10¹⁰, 2.3 × 10⁹ and 4.7 × 10⁹ M^?1sec^?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co⁺⁺) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that G_eaq- ∽ _H ⁺ G_oH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs.     

Design,synthesis, characterization,and biological evaluation of pyrido[1,2-a]pyrimidinone coumarins as promising anti-inflammatory agents

Pursuing our recent interest regarding antimicrobial and anti-inflammatory activities of coumarin derivatives, we have synthesized a series of coumarin-linked pyridopyrimidinones by using Baylis Hillman adduct in aqueous condition with high purity. Pyrido[1,2-a]pyrimidin-2-ones are important class of heterocyclic compounds because of their use in medicinal and agro chemistry as active agents. All these newly synthesized compounds were evaluated for their antimicrobial and anti-inflammatory activity. Coumarin pyridopyrimidinones showed excellent anti-inflammatory activity against both MMP-2 and MMP-9 gelatinase zymography, whereas considerable good activity against Gram-positive and Gram-negative bacterial strains; however, antifungal activity observed in these series is more or less inactive. The active compounds of these series would be promising structural templates for the development of novel and more efficient anti-inflammatory agent.     

Large Femtosecond Two-Photon Absorption Cross-Sections of Fullerosome Vesicle Nanostructures Derived from Highly Photoresponsive Amphiphilic C(60)-Light-Harvesting Fluorene Dyad

We demonstrated ultrafast femtosecond nonlinear optical (NLO) absorption characteristics of bilayered fullerosome vesicle nanostructures derived from molecular self-assembly of amphiphilic oligo(ethylene glycolated) C(60)-(light-harvesting diphenylaminofluorene antenna). Fullerene conjugates were designed to enhance photoresponse in a femtosecond time scale by applying an isomerizable periconjugation linker between the C(60) cage and diphenylaminofluorene antenna subunit in an intramolecular contact distance of only < 3.0 ?. Morphology of C(60)(>DPAF-EG(12)C(1))-based fullerosome nanovesicles in H(2)O was characterized to consist of a bilayered shell with a sphere diameter of 20-70 nm and a chromophore shell-width of 9.0-10 nm, fitting well with a head-to-head packing configuration of the molecular length. At the estimated effective nanovesicle concentration as low as 5.5 × 10(-8) MV (molecular molar concentration of 5.0 × 10(-4) M) in H(2)O, two-photon absorption (2PA) phenomena were found to be the dominating photophysical events showing a large molar concentration-insensitive 2PA cross-section value equivalent to 8500 GM in a form of nanovesicles, on average. The observed NLO characteristics led to a sharp trend of efficient light-transmittance intensity reduction at the input laser intensity above 100 GW/cm(2).     

The Synthesis and Biological Evaluation of Regioisomeric Benzothiazolyl Coumarins

Various 4-aryloxymethylcoumarins have been obtained by the r.t. allylic substitution with formylphenols. These have been further reacted with o-aminothiophenol resulting in the formation of a benzothiazole skeleton. These compounds have been synthesised with a view to study their potential as microbial growth inhibitors. Comparative studies on the spectral and antimicrobial activities have also been carried out.     

First Thermal Chemoselective Synthesis of Novel 2′,3′‐Dihydro‐3′‐Hydroxy‐benzofuranylcoumarins

An attempted reaction of 4‐bromomethylcoumarin with 2‐hydroxy aromatic aldehyde/2‐hydroxy aromatic ketone at room temperature in the presence of a mild base resulted in the formation of cis‐2′,3′‐dihydro‐3‐hydroxybenzofuranylcoumarins by carbanion addition across the carbonyl carbon.     

Effects of Base for the Efficient Synthesis of 4-Formylcoumarins and 4-Formylcarbostyrils

The first efficient transformation of 4-bromomethylcoumarins and 4-bromomethylcarbostyrils to 4-formylcoumarins and 4-formylcarbostyril under aqueous conditions has been achieved by modifying the Kornblum method, resulting in excellent yield. The experimental method is very simple and economical; no further purification is required and the experimental conditions have been optimized. All the isolated compounds were characterized by infrared, NMR, and mass spectroscopy, and some of the compounds have been analyzed by single-crystal x-ray analysis.     

Synthesis of Naked-eye Detectable Fluorescent 2<Emphasis Type="Italic">H-</Emphasis>chromen-2-One 2, 6-Dicyanoanilines: Effect of Substituents and pH on Its Luminous Behavior

A variety of new coumarin derivatives containing C-4 bridged 2,6-dicyanoanilines (4a-4d) were synthesized via multicomponent one pot approach. These novel sensors were characterized by spectral analysis and a series of pH sensing fluorescence studies were performed, the results indicating that the sensors are highly selective and more effective at various pH. The fluorescence colour changes at different pH could be directly detected by naked eyes.     

Spanning trees with many leaves in cubic graphs

For a connected graph G let L(G) denote the maximum number of leaves in any spanning tree of G. We give a simple construction and a complete proof of a result of Storer that if G is a connected cubic graph on n vertices, then L(G) ? [(n/4) + 2], and this is best possible for all (even) n. The main idea is to count the number of “dead leaves” as the tree is being constructed. This method of amortized analysis is used to prove the new result that if G is also 3-connected, then L(G) ? [(n/3) + (4/3)], which is best possible for many n. This bound holds more generally for any connected cubic graph that contains no subgraph K₄ - e. The proof is rather elaborate since several reducible configurations need to be eliminated before proceeding with the many tricky cases in the construction.