Elucidating the intermolecular hydrogen bonding interaction of proline with amides—quantum chemical calculations

Structural Chemistry - The hydrogen-bonded complexes formed between proline and amides have been investigated completely by the use of computational methods such as Atoms In Molecules (AIM),...     

Synthesis and characterization of dimeric μ-oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Two vanadium (IV) complexes [V^IVO(Haeae-sal)(MeOH)]⁺ ( 1 ) and [V^IVO(Haeae-hyap)(MeOH)]⁺ ( 2 ) were prepared by reacting [VO(acac)₂] with ligands [H₂aeae-sal] ( I ) and [H₂aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 10² h⁻¹) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 10² h⁻¹) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 10⁴ h⁻¹ whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 10³ h⁻¹ for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.     

Chemically characterised Pimenta dioica (L.) Merr. essential oil as a novel plant based antimicrobial against fungal and aflatoxin B1 contamination of stored maize and its possible mode of action

Abstract

The chemical characterisation of Pimenta dioica essential oil (PDEO) revealed the presence of 50 components, amongst which α-Terpineol (30.31%) was the major component followed by β-Linalool (6.75%) and γ-Terpinene (4.64%). The oil completely inhibited the growth of aflatoxin B₁ secreting strain Aspergillus flavus LHP-VS-8 and aflatoxin B₁ production at 2.5?µL/mL and 1.5?µL/mL, respectively. The oil caused dose dependent reduction of methylglyoxal (an AFB₁ inducer), enhanced leakage of Ca²⁺, Mg²⁺ and K⁺ ions and significantly reduced ergosterol content of fungal plasma membrane. During in situ experiments, PDEO exhibited complete protection of fumigated maize cob slices from fungal infestation without affecting seed germination. The chemically characterised PDEO is recommended as a plant based preservative and shelf life enhancer of food commodities by preventing fungal growth, AFB₁ production and lipid peroxidation. This is the first report on PDEO as inhibitor of AFB₁ secretion and methylglyoxal biosynthesis.     

Viscous flow in a mixed compression intake

Numerical simulation of the flow in a two‐dimensional mixed compression intake is carried out by solving unsteady viscous compressible equations using a stabilized finite element method. The effect of bleed in starting/unstarting of the intake and controlling the buzz instability is investigated in detail. Higher bleed leads to an increase in the ability of the intake to sustain larger back‐pressure for stable operation. The amount of bleed and its location is varied to understand its effect on the performance of the intake. Two kinds of unsteady oscillations are observed: ‘little’ and ‘big’ buzz. The frequency of the both kinds of buzz oscillations is found to be super‐harmonic of the fundamental acoustic frequency of intake modeled as an open‐closed organ pipe. The frequency as well as amplitudes of the big buzz cycles is larger than those of the little buzz. The little‐ and big‐buzz are found to occur for low‐ and high‐subcritical state of the intake and are very similar to Ferri and Dailey criteria, respectively. Buzz is eliminated when relatively high bleed is implemented, both, upstream and downstream of the throat. The effect of rate of change of back‐pressure on the start/unstart of the intake is investigated. Two situations are considered. The first case is that of an intake where the back‐pressure remains below the critical value. It is found that the intake remains started if the change in back‐pressure is gradual. However, it unstarts if the back‐pressure is changed relatively rapidly. The second set of simulations is an attempt to model the situation where the back‐pressure at the exit of the intake exceeds the critical value and a logic is incorporated in the feed back loop of the fuel modulation to start the intake. Low rate of change of pressure is unsuccessful in starting the intake. Relatively high rates result in either a quick starting of the intake or a slow unstart. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of five-membered N-heterocycles using silver metal

The heterocyclic chemistry field has been revolutionized using transition metal catalyst in recent years. Various research groups have focused on the development of general protocols to achieve better functional group compatibilities and greater levels of molecular complexity under mild reaction conditions using easily available starting substrates. These methods afford many advantages as compared to alternative pathways involved in the synthesis of heterocyclic compounds. In this review article, we have concentrated on the synthesis of nitrogen-containing five-membered heterocylces in the presence of silver catalyst.     

Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation

Sum-frequency-generation (SFG) vibration spectroscopy is a technique only sensitive to functional groups arranged without centrosymmetry. For crystalline cellulose, SFG can detect the C6H₂ and intra-chain hydrogen-bonded OH groups in the crystal. The geometries of these groups are sensitive to the hydrogen bonding network that stabilizes each cellulose polymorph. Therefore, SFG can distinguish cellulose polymorphs (I_β, II, III_I and III_II) which have different conformations of the exocyclic hydroxymethylene group or directionalities of glucan chains. The C6H₂ asymmetric stretching peaks at 2,944 cm^?1 for cellulose I_β and 2,960 cm^?1 for cellulose II, III_I and III_II corresponds to the trans-gauche (tg) and gauche-trans (gt) conformation, respectively. The SFG intensity of the stretch peak of intra-chain hydrogen-bonded O–H group implies that the chain arrangement in cellulose crystal is parallel in I_β and III_I, and antiparallel in II and III_II.