THE EFFECTS OF NEAR-UV RADIATION ON HUMAN LENS β-CRYSTALLINS: PROTEIN STRUCTURAL CHANGES and THE PRODUCTION OF O2_ and H2O2

beta-Crystallins (beta 1-, beta 2- and beta 3-crystallin) comprise nearly half the protein of the human lens. The effect of near-UV radiation, which is one of the possible risk factors in cataract formation, on the beta-crystallins is investigated in this study. Protein intersubunit crosslinking, change in charge of the protein subunits to more acidic species and changes in protein tertiary structure (conformation) by 300 nm irradiation are reported. The fluorescence yield of protein tryptophan residues decreases by 300 nm irradiation. There is an increase in nontryptophan fluorescence (lambda cx 340 nm, lambda cm 400-600 nm), and in protein absorption at 340 nm, due to the formation of tryptophan photooxidation products. Both tryptophan and its oxidation products can be photoexcited by 300 nm irradiation and the latter are known to be good photosensitizers. The results provide evidence for the generation of H2O2 in the irradiated human beta-crystallin solutions by the Type I photosensitizing action of the chromophores absorbing at 300 nm. The H2O2 is generated via the intermediate production of O2 anion; the latter spontaneously dismutates to H2O2, presumably via O2- protein interactions. The amount of H2O2 generated per absorbed photon is compared for various solutions of beta 1-, beta 2- and beta 3-crystallins from human lenses of different age.     

Condensed cyclic and bridged-ring systems : part 12: A novel synthetic route to 4-p-methoxyphenyl-bicyclo[ 2.2.2 ]octan-2-ones and some bicyclo [ 3.2.1 ] octane derivatives by acid-catalyzed intramolecula

The efficacy of a new acid-catalyzed intramolecular C-alkylation has been demonstrated by the synthesis of 1-methyl-4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{5}$) and 4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{6}$) from easily accessible starting materials. The carbinol $\text{20}$, derived from $\text{5}$, undergoes facile rearrangement leading to 1-$\text{p}$-methoxyphenyl-4-methyl bicyclo [3.2.1] oct-3-ene ($\text{22}$), which has been transformed to $\text{endo}$-1-$\text{p}$-methoxyphenyl-4-methylbicyclo [3.2.1] octan-3-one ($\text{25}$).     

Synthesis of (±)-2-Methoxy-9a-Carbamorphinan and (±)-2-Methoxy-9a-Carba-14α-Morphinan: Acid Catalyzed Cyclizations of 1-m-Methoxybenzyl-4, 4a,5,6,7,8-Hexahydronaphthalen-2(3H)-ONE and 1 -m-Methox Ybenzyloctalins

The bridged-ethers, (±)-2-methoxy-9a-carbamorphinan (1b) and (±)-2-methoxy-9a-carba-14α-morphinan(2b) have been synthesized. The acid-catalyzed cyclizations of 1-m-methoxy benzyloctalone 3b and 1-m-methoxybenzyloctalins 4b proceed with high regio-and stereoselectivities leading mostly to the bridged-ketone 14 and ether 1b respectively, along with o-methoxy-tetracyclic ketone 15 and the ether 17, in addition to other minor products.     

Conformational flexibility of xanthene‐based covalently linked dimers

The conformational flexibility of three covalently linked dimers consisting of two xanthene‐based moieties connected by a diphenyl ether linker was studied using NMR spectroscopy, X‐ray crystallography, and density functional theory (DFT) calculations. The three dimers interconvert as a function of pH: the doubly cationic dimer (Xan⁺)₂ exists in acidic solutions (pH < 0.5), the mono‐alcohol monocation Xan⁺–Xan‐OH at intermediate pH values (pH = 1–3), and the neutral diol at the highest pH‐values (pH > 3). Each dimer exhibits conformational degrees of freedom associated with rotations of either the xanthene moiety or of the diphenyl ether (DPE) linker. The barriers for rotation of the xanthylium moiety were evaluated using DFT calculations, yielding values of 23 kcal/mol for (Xan⁺)₂ and 11 kcal/mol for (Xan‐OH)₂, respectively. The rotational barrier for the diphenyl ether linker in Xan⁺–Xan‐OH (15 kcal/mol) was experimentally determined using variable temperature NMR measurements. The relative orientation of the two –OH groups in (Xan‐OH)₂ diol was investigated in solution and the solid state using NMR spectroscopy and X‐ray crystallography. The conformer observed in the solid state was found to be the In–Out conformer, while free rotation of the xanthenol units is thought to occur on the NMR timescale at room temperature. These studies are relevant for the design of linkers for efficient water oxidation catalysts. Copyright © 2016 John Wiley & Sons, Ltd.     

A conceptual high flux reactor design with scope for use in ADS applications

A 100 MWt reactor design has been conceived to support flux level of the order of 10¹⁵ n/cm²/s in selected flux trap zones. The physics design considers high enriched metallic alloy fuel in the form of annular plates placed in a D₂O moderator tank in a hexagonal lattice arrangement. By choosing a tight lattice pitch in the central region and double the lattice pitch in the outer region, it is possible to have both high fast flux and thermal flux trap zones. By design the flux level in the seed fuel has been kept lower than in the high flux trap zones so that the burning rate of the seed is reduced. Another important objective of the design is to maximize the time interval of refueling. As against a typical refueling interval of a few weeks in such high flux reactor cores, it is desired to maximize this period to as much as six months or even one year. This is possible to achieve by eliminating the conventional control absorbers and replacing them with a suitable amount of fertile material loading in the reactor. Requisite number of seedless thorium-aluminum alloy plates are placed at regular lattice locations vacated by seed fuel in alternate fuel layers. It is seen that these thorium plates are capable of acquiring asymptotic fissile content of 14 g/kg in about 100 days of irradiation at a flux level of 8 × 10¹⁴ n/cm²/s. In summary, the core has a relatively higher fast flux in the central region and high thermal flux in the outer region. The present physics design envisages a flat core excess reactivity for the longest possible cycle length of 6 months to one year. It is also possible to modify the design for constant subcriticality for about the same period or longer duration by considering neutron spallation source at the centre and curtailing the power density in the inner core region by shielding it with a layer of thoria fuel loading.      

Vector bundles with a fixed determinant on an irreducible nodal curve

LetM be the moduli space of generalized parabolic bundles (GPBs) of rankr and degree dona smooth curveX. LetM _−L be the closure of its subset consisting of GPBs with fixed determinant− L. We define a moduli functor for whichM _−L is the coarse moduli scheme. Using the correspondence between GPBs onX and torsion-free sheaves on a nodal curveY of whichX is a desingularization, we show thatM _−L can be regarded as the compactified moduli scheme of vector bundles onY with fixed determinant. We get a natural scheme structure on the closure of the subset consisting of torsion-free sheaves with a fixed determinant in the moduli space of torsion-free sheaves onY. The relation to Seshadri-Nagaraj conjecture is studied.     

Numerical study of concentrated fluid–particle suspension flow in a wavy channel

The particle migration effects and fluid–particle interactions occurring in the flow of highly concentrated fluid–particle suspension in a spatially modulated channel have been investigated numerically using a finite volume method. The mathematical model is based on the momentum and continuity equations for the suspension flow and a constitutive equation accounting for the effects of shear‐induced particle migration in concentrated suspensions. The model couples a Newtonian stress/shear rate relationship with a shear‐induced migration model of the suspended particles in which the local effective viscosity is dependent on the local volume fraction of solids. The numerical procedure employs finite volume method and the formulation is based on diffuse‐flux model. Semi‐implicit method for pressure linked equations has been used to solve the resulting governing equations along with appropriate boundary conditions. The numerical results are validated with the analytical expressions for concentrated suspension flow in a plane channel. The results demonstrate strong particle migration towards the centre of the channel and an increasing blunting of velocity profiles with increase in initial particle concentration. In the case of a stenosed channel, the particle concentration is lowest at the site of maximum constriction, whereas a strong accumulation of particles is observed in the recirculation zone downstream of the stenosis. The numerical procedure applied to investigate the effects of concentrated suspension flow in a wavy passage shows that the solid particles migrate from regions of high shear rate to low shear rate with low velocities and this phenomenon is strongly influenced by Reynolds numbers and initial particle concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

PrincipalG-bundles on nodal curves

LetG be a connected semisimple affine algebraic group defined over C. We study the relation between stable, semistable G-bundles on a nodal curveY and representations of the fundamental group ofY. This study is done by extending the notion of (generalized) parabolic vector bundles to principal G-bundles on the desingularizationC ofY and using the correspondence between them and principal G-bundles onY. We give an isomorphism of the stack of generalized parabolic bundles onC with a quotient stack associated to loop groups. We show that if G is simple and simply connected then the Picard group of the stack of principal G-bundles onY is isomorphic to ⊕_m Z,m being the number of components ofY.