Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation

The diphosphazane ligands of the type, (C20H12O2)PN(R)P(E)Y2 (R = CHMe2 or (S)-*CHMePh; E = lone pair or S; Y2 = O2C20H12 or Y = OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl2{ηsu2}-((O2C20H12)PN((S)-*CHMePh)PPh2] has been determined by X-ray crystallography. The reactions of [CpRu(PPh3)2Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X2PN(R)PYY′ (R = CHMe2 or (S)-*CHMePh; X = C6H5 or X2 = O2C20H12; Y=Y′= C6H5 or Y = C6H5, Y′ = OC6H4Me-4 or OC6H3Me2-3,5 or N2C3HMe2-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη2-Ph2PN((S)-*CHMePh)*PPh (N2C3HMe2-3,5)Cl] is established by X-ray diffraction. The reactions of Ru3(CO)12 with the diphosphazanes (C20H12O2)PN(R)PY2 (R = CHMe2orMe; Y2=O2C20H12or Y= OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) yield the triruthenium clusters [Ru3(CO)10{η-(O2C20H12)PN(R)PY2}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η3-allyl palladium complexes, [Pd(η3-l,3-R′2-C3H3){η2-(rac)-(02C20H12)PN(CHMe2)PY2}](PF6) (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.

Effect of solvents on the enzyme mediated degradation of copolymers

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 degrees C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.

Effect of solvents on the enzyme mediated degradation of copolymers

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 degrees C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.