Gauge generators,transformations and identities on a noncommutative space

By abstracting a connection between gauge symmetry and gauge identity on a noncommutative space, we analyse star (deformed) gauge transformations with the usual Leibniz rule as well as undeformed gauge transformations with a twisted Leibniz rule. Explicit structures of the gauge generators in either case are computed. It is shown that, in the former case, the relation mapping the generator with the gauge identity is a star deformation of the commutative space result. In the latter case, on the other hand, this relation gets twisted to yield the desired map.     

Coupling effects of resonant and discretized non-resonant continuum states in 4He + 6Li scattering at 10 MeV/A

Alpha-particle scattering from the resonant (3 ₁ ⁺ ) and non-resonant continuum states of ⁶Li is studied at incident energy 10 MeV/A. The α + d breakup continuum part within the excitation energy E _ex = 1.475–2.475 MeV is discretized in two energy bins. Unlike the results at higher incident energies, here the coupled-channel calculations show significant breakup continuum coupling effects on the elastic and inelastic scattering. It is shown that even when the continuum-continuum coupling effects are strong, the experimental data of the ground state and the resonant as well as discretized non-resonant continuum states impose stringent constraint on the coupling strengths of the non-resonant continuum states.     

Hydrated titanium(IV) oxide as a granular inorganic sorbent for removal of radiostrontium

The sorption of radiostrontium on hydrated titanium(IV) oxide was studied in batch equilibration experiments. The strontium uptake capacity was determined. Batch distribution coefficients were measured as function of solution pH as well as strontium and sodium concentration. The effect of electron beam irradiation on strontium sorption was also examined. The results are of significance in connection with the removal of radiostrontium traces from alkaline sodium salt-loaded wastes of reprocessing plant origin.     

Monomer chain-transfer constants from emulsion copolymerization data: Styrene and α-methylstyrene

Radical chain-transfer constants can be deduced from corresponding measurements of rates and degrees of polymerization in copolymerization experiments. It is particularly useful to carry out such copolymerization in emulsion systems where the normal termination reactions are relatively less important and chain-transfer processes are significant in determining the number-average degree of polymerization. The method is illustrated for copolymerization of styrene and α-methylstyrene at three temperatures. Rate constants for transfer of styryl and α-methylstyryl radicals to either monomer were measured. All the rate constants are consistent with the relative stabilities of the product radicals which could be formed by the various transfer reactions. The procedure described here can be extended for measurements of rate constants for reactions of other potential transfer agents.     

Synthesis, characterization, and reactivity of mononuclear O,N-chelated vanadium(IV) and -(III) complexes of methyl 2-Aminocyclopent-1-ene-1-dithiocarboxylate based ligand: reporting an example of conformational isomerism in the solid state

Vanadium(IV) and -(III) complexes of a tetradentate N(2)OS Schiff base ligand H(2)L [derived from methyl 2-((beta-aminoethyl)amino)cyclopent-1-ene-1-dithiocarboxylate and salicylaldehyde] are reported. In all the complexes, the ligand acts in a bidentate (N,O) fashion leaving a part containing the N,S donor set uncoordinated. The oxovanadium(IV) complex [VO(HL)(2)] (1) is obtained by the reaction between [VO(acac)(2)] and H(2)L. In the solid state, compound 1 has two conformational isomers 1a and 1b; both have been characterized by X-ray crystallography. Compound 1a has the syn conformation that enforces the donor atoms around the metal center to adopt a distorted tbp structure (tau = 0.55). Isomer 1b on the other hand has an anti conformation with almost a regular square pyramidal geometry (tau = 0.06) around vanadium. In solution, however, 1 prefers to be in the square pyramidal form. A second variety of vanadyl complex [VO(L(cyclic))(2)](I(3))(2) (2) with a new bidentate O,N donor ligand involving isothiazolium moiety has been obtained by a ligand-based oxidation of the precursor complex 1 with iodine. Preliminary X-ray and FAB mass spectroscopic data of 2 have supported the formation of a heterocyclic moiety by a ring closure reaction involving a N-S bond. Vanadium(III) complex [V(acac)(HL)(2)] (3) has been obtained through partial ligand displacement of [V(acac)(3)] with H(2)L. Compound 3 has almost a regular octahedral structure completed by two bidentate HL ligands along with an acetylacetonate molecule. Electronic spectra, magnetism, EPR, and redox properties of these compounds are reported.     

A Post‐Synthetically Modified MOF for Selective and Sensitive Aqueous‐Phase Detection of Highly Toxic Cyanide Ions

Selective and sensitive detection of toxic cyanide (CN^?) by a post‐synthetically altered metal–organic framework (MOF) has been achieved. A post‐synthetic modification was employed in the MOF to incorporate the specific recognition site with the CN^? ion over all other anions, such as Cl^?, Br^?, and SCN^?. The aqueous‐phase sensing and very low detection limit, the essential prerequisites for an effective sensory material, have been fulfilled by the MOF. Moreover, the present detection level meets the standard set by the World Health Organization (WHO) for the permissible limit of cyanide concentration in drinking water. The utilization of MOF‐based materials as the fluorometric probes for selective and sensitive detection of CN^? ions has not been explored till now.     

Intramolecular O-H...O hydrogen-bond-mediated reversal in the partitioning of conformationally restricted triplet 1,4-biradicals and amplification of diastereodifferentiation in their lifetimes

The photoreactivity and nanosecond transient phenomena have been investigated for a rationally designed set of ketones 4-9 in order to gain comprehensive insights concerning the influence of intramolecular hydrogen bonding on (i) the lifetimes of triplet 1,4-biradicals and (ii) the partitioning of the latter between cyclization and elimination. Comparisons of the photochemical results and lifetime data for the biradicals of ketones 6 versus 8 and 7 versus 9 revealed a remarkable influence of hydrogen bonding when superimposed upon steric factors: while 6 and 7 yielded cyclobutanols in poor yields, cyclization was found to be overwhelmingly predominant for 8-anti and moderately so for 9-anti, with a high stereoselectivity in the formation of cyclobutanols (>95% for 8-anti). The diastereochemistry in the case of 8 permitted the occurrence of fragmentation or cyclization almost exclusively (>90% cyclization for 8-anti and >75% elimination for 8-syn). Significantly, the intramolecular hydrogen bonding in the biradicals of 8 and 9 was found to reverse their partitioning between cyclization and elimination compared with the behavior of the biradicals of ketones 3; the ketones 8-anti and 9-anti underwent cyclization in benzene, predominantly leading to cyclobutanols with syn stereochemistry between the C2 and C3 substituents. In accordance with photoproduct profiles, an unprecedented approximately 2-fold difference in the lifetimes of the intermediate diastereomeric triplet biradicals of ketones 8 in nonpolar solvents (e.g., tau(syn) = 123 ns and tau(anti) = 235 ns in cyclohexane) was observed via nanosecond laser flash photolysis, while no such difference in lifetimes was found for the triplet biradicals of acetoxy ketones 9. The intriguing diastereodifferentiation in the lifetimes of the diastereomeric triplet 1,4-biradicals of 8 and the product profiles of ketones 6, 7, and 9 are best reconciled via a unified mechanistic picture in which superposition of steric factors over varying magnitudes of O-H...O hydrogen bonding selectively facilitates a particular pathway. In particular, the diastereodifferentiation in the photochemical outcomes for the diastereomers of ketone 8 and in the lifetimes of their triplet biradicals can be understood on the basis of rapid deactivation of the 8-syn triplet biradical via fragmentation and slow cyclization of the 8-anti triplet biradical from chair- and twist-boat-like hydrogen-bonded conformations, respectively. The photolysis in polar aprotic solvents such as DMSO and pyridine was found to reverse the chemoselectivity, yielding reactivity paralleling that of ketones 3, for which the steric factors between the C2 and C3 substituents control the photochemical outcome.     

Excited-state proton-transfer dynamics of 7-hydroxyquinoline in room temperature ionic liquids

Excited-state proton transfer (ESPT) reaction of 7-hydroxyquinoline (7-HQ) mediated by methanol molecules has been studied in two room temperature ionic liquids (RTILs) using steady-state and time-resolved fluorescence measurements. While no ESPT is observable in neat RTILs, characteristic tautomer fluorescence of 7-HQ could be observed in the presence of small quantity of methanol (0.5-4.1 M). The observation of a rise time (350 ps-1.4 ns) associated with the tautomer fluorescence suggests that proton transfer in 7-HQ is indeed an excited-state phenomenon that requires considerable solvent reorganization prior to the relay of proton from the hydroxyl group to the distant ring nitrogen atom through suitably organized dimeric chain of methanol molecules. The rise time of the tautomer fluorescence, which has been found to decrease with increasing methanol concentration, is attributed to the change of viscosity of the medium upon methanol addition. While the influence of viscosity on the ESPT kinetics is evident from the data, lack of any definite correlation between the bulk viscosity and the rise time has been interpreted in terms of the microheterogeneous nature of the media that does not allow assessment of the microviscosity around 7-HQ from the bulk viscosity.     

Polarity dependence of the radiative and nonradiative rates of flavone derivatives comprising structurally similar amino moieties: change in the nature of the emitting state

Photophysical behavior of several structurally related electron donor-acceptor flavone derivatives, which have been synthesized and characterized, has been studied as a function of the polarity of the media. Significant variation of the absorption and fluorescence response of the systems has been observed with change in the polarity of the medium. The results show an increase in the radiative rate constant and a decrease in the nonradiative rate constant of the systems with increase in the polarity of the media. This finding has been attributed to the change in the nature of the emitting state from a mixed n-pi* and pi-pi* state to a dominant pi-pi* state with increase in the polarity of the medium. The results of single-crystal diffraction studies and theoretical calculations based on density functional method support the idea of close proximity of the n-pi* and pi-pi* states and the change in their relative contributions toward the emission process with the polarity of the medium. Laser flash photolysis studies show that the triplet state is not involved in the variation of the fluorescence response of the systems.