Enantioselective Formal C(sp2)−H Vinylation

An enantioselective formal C(sp²)?H vinylation of prochiral 2,2‐disubstituted cyclopentene‐1,3‐dione is presented. This vinylative desymmetrization is realized by using a two‐step procedure that consists of a catalytic enantioselective vinylogous Michael addition of deconjugated butenolides to cyclopentene‐1,3‐dione and a base‐mediated decarboxylation. The overall process utilizes deconjugated butenolides as the source of the highly substituted vinyl unit. Five‐membered carbocycles containing a remote all‐carbon quaternary stereogenic center are obtained in good yields and with good to high enantioselectivities.     

Example of highly stereoregulated ruthenium amidine complex formation: synthesis,crystal structures,and spectral and redox properties of the complexes [Ru(II)(trpy)[NC(5)H(4)-CH=N-N(C(6)H(5))C(CH(3))=NH]](ClO(4))(2) (1) and [Ru(II)(trpy)(NC(5)H(4)-CH=N-NH-C(6)H(5))Cl]ClO(4) (2) (trpy = 2,2':6',2"-terpyridine)

The reaction of Ru(trpy)Cl(3) (trpy = 2,2':6',2"-terpyridine) with the pyridine-based imine function N(p)C(5)H(4)-CH=N(i)-NH-C(6)H(5) (L), incorporating an NH spacer between the imine nitrogen (N(i)) and the pendant phenyl ring, in ethanol medium followed by chromatographic work up on a neutral alumina column using CH(3)CN/CH(2)Cl(2) (1:4) as eluent, results in complexes of the types [Ru(trpy)(L')](ClO(4))(2) (1) and [Ru(trpy)(L)Cl]ClO(4) (2). Although the identity of the free ligand (L) has been retained in complex 2, the preformed imine-based potentially bidentate ligand (L) has been selectively transformed into a new class of unusual imine-amidine-based tridentate ligand, N(p)C(5)H(4)-CH=N(i)-N(C(6)H(5))C(CH(3))=N(a)H (L'), in 1. The single-crystal X-ray structures of the free ligand (L) and both complexes 1 and 2 have been determined. In 2, the sixth coordination site, that is, the Cl(-) function, is cis to the pyridine nitrogen (N(p)) of L which in turn places the NH spacer away from the Ru-Cl bond, whereas, in 1, the corresponding sixth position, that is, the Ru-N(a) (amidine) bond, is trans to the pyridine nitrogen (N(p)) of L'. The trans configuration of N(a) with respect to the N(p) of L' in 1 provides the basis for the selective L --> L' transformation in 1. The complexes exhibit strong Ru(II) --> pi* (trpy) MLCT transitions in the visible region and intraligand transitions in the UV region. The lowest energy MLCT band at 510 nm for 2 has been substantially blue-shifted to 478 nm in the case of 1. The reversible Ru(III)-Ru(II) couples for 1 and 2 have been observed at 0.80 and 0.59 V versus SCE, respectively. The complexes are weakly luminescent at 77 K, exhibiting emissions at lambda(max), 598 nm [quantum yield (Phi) = 0.43 x 10(-2)] and 574 nm (Phi = 0.28 x 10(-2)) for 1 and 2, respectively.     

The molecular structure of N-hydroxyurea

Ab initio calculations were performed on the tautomers and conformers of N-hydroxyurea using a 6-31G ** basis set. The minimum-energy structures have been found and the importance of the intramolecular hydrogen bond as the stabilizing factor was pointed out. © 1996 John Wiley & Sons, Inc.     

Induction of phr gene expression in E. coli strain KY706/pPL-1 by He–Ne laser (632.8 nm) irradiation

We have observed that He–Ne laser irradiation of E. coli strain KY706/pPL-1 leads to induction of photolyase gene, phr. The magnitude of induction was found to depend on the He–Ne laser fluence, fluence rate and post-irradiation incubation period in the nutrient medium. The optimum values for fluence and fluence rate were 7×10³ J/m² and 100 W/m², respectively, and the induction of phr gene was observed to saturate beyond an incubation period of 2 h. Experiments carried out with singlet oxygen quenchers and with D₂O suggest that the effect is mediated via singlet oxygen. Photoreactivation studies carried out after UVC exposure of both the He–Ne laser-exposed as well as unexposed cells showed a larger surviving fraction in the He–Ne laser pre-irradiated cells. This can be attributed to He–Ne laser irradiation-induced induction of phr expression. However, since even without photoreactivating light He–Ne laser pre-irradiated cells show higher survival against UVC radiation it appears that He–Ne laser irradiation induces both light-dependent as well as dark DNA repair processes.     

The physics of accelerator driven sub-critical reactors

In recent years, there has been an increasing worldwide interest in accelerator driven systems (ADS) due to their perceived superior safety characteristics and their potential for burning actinides and long-lived fission products. Indian interest in ADS has an additional dimension, which is related to our planned large-scale thorium utilization for future nuclear energy generation. The physics of ADS is quite different from that of critical reactors. As such, physics studies on ADS reactors are necessary for gaining an understanding of these systems. Development of theoretical tools and experimental facilities for studying the physics of ADS reactors constitute important aspect of the ADS development program at BARC. This includes computer codes for burnup studies based on transport theory and Monte Carlo methods, codes for studying the kinetics of ADS and sub-critical facilities driven by 14 MeV neutron generators for ADS experiments and development of sub-criticality measurement methods. The paper discusses the physics issues specific to ADS reactors and presents the status of the reactor physics program and some of the ADS concepts under study.      

Precise toppling balance, quenched disorder, and universality for sandpiles

A single sandpile model with quenched random toppling matrices captures the crucial features of different models of self-organized criticality. With symmetric matrices avalanche statistics falls in the multiscaling Bak-Tang-Wiesenfeld universality class. In the asymmetric case the simple scaling of the Manna model is observed. The presence or absence of a precise toppling balance between the amount of sand released by a toppling site and the total quantity the same site receives when all its neighbors topple once determines the appropriate universality class.     

Engineering bands of extended electronic states in a class of topologically disordered and quasiperiodic lattices

We show that a discrete tight-binding model representing either a random or a quasiperiodic array of bonds can have the entire energy spectrum or a substantial part of it absolutely continuous, populated by extended eigenfunctions only, when atomic sites are coupled to the lattice locally, or non-locally from one side. The event can be fine-tuned by controlling only the host–adatom coupling in one case, while in two other cases cited here an additional external magnetic field is necessary. The delocalization of electronic states for the group of systems presented here is sensitive to a subtle correlation between the numerical values of the Hamiltonian parameters – a fact that is not common in the conventional cases of Anderson localization. Our results are analytically exact, and supported by numerical evaluation of the density of states and electronic transmission coefficient.