Structured Surfaces for Generation of Negative Index of Refraction

Materials with negative index of refraction have properties that are not naturally available. Such properties can be used to develop novel devices like the superlens which can surpass the diffraction limit. Optical cloaking can be achieved through this negative refractive index method. This article reviews the progress made in the area of negative refractive index materials from the first generation of negative electrical permittivity to the demonstration of negative index of refraction at optical frequency, with the relevant discussion on the physics of these materials. The prime focus of this article is on experimental demonstrations and fabrication related issues of negative refractive index materials which makes use of structured surfaces.     

Faithful actions of locally compact quantum groups on classical spaces

We construct examples of locally compact quantum groups coming from bicrossed product construction, including non-Kac ones, which can faithfully and ergodically act on connected classical (noncompact) smooth manifolds. However, none of these actions can be isometric in the sense of Goswami (Commun Math Phys 285(1):141–160, 2009), leading to the conjecture that the result obtained by Goswami and Joardar (Rigidity of action of compact quantum groups on compact, connected manifolds, 2013. arXiv:1309.1294) about nonexistence of genuine quantum isometry of classical compact connected Riemannian manifolds may hold in the noncompact case as well.     

Observation of enhanced orbital electron-capture nuclear decay rate in a compact medium

The eigenstate energies of an atom increase under spatial confinement and this effect should increase the electron density of the orbital electrons at the nucleus thus increasing the decay rate of an electron capturing radioactive nucleus. We have observed that the orbital electron capture rates of ¹⁰⁹In and ¹¹⁰Sn increased by (1.00±0.17)%$(1.00\pm 0.17)\mathrm{\%}$ and (0.48±0.25)%$(0.48\pm 0.25)\mathrm{\%}$ respectively when implanted in the smaller Au lattice compared to implantation in a larger Pb lattice. These observations are interpreted to be a result of the higher compression experienced by the large radioactive atoms in the smaller spatial confinement of the Au lattice.     

Non-destructive assay technique for the determination of <Superscript>238</Superscript>U/<Superscript>232</Superscript>Th ratio in the mixed oxides of uranium and thorium using prompt gamma-ray neutron activation

A non-destructive assay technique based on prompt gamma-ray neutron activation analysis for the determination of ²³⁸U to ²³²Th ratio in the mixed oxide fuel materials has been established. The method uses closely spaced high energy gamma-rays in the region of 4000 keV to 4150 keV enabling it to be applied for samples of any geometry and thickness without having any correction for gamma-ray attenuations and detection efficiencies.     

Control of laser induced molecular fragmentation of n-propyl benzene using chirped femtosecond laser pulses

We present the effect of chirping a femtosecond laser pulse on the fragmentation of n-propyl benzene. An enhancement of an order of magnitude for the relative yields of and in the case of negatively chirped pulses and in the case of positively chirped pulses with respect to the transform-limited pulse indicates that in some fragmentation channel, coherence of the laser field plays an important role. For the relative yield of all other heavier fragment ions, resulting from the interaction of the intense laser field with the molecule, there is no such enhancement effect with the sign of chirp, within experimental errors. The importance of the laser phase is further reinforced through a direct comparison of the fragmentation results with the second harmonic of the chirped laser pulse with identical bandwidth.     

Photosensitizers derived from 132-oxo-methyl pyropheophorbide-a: enhanced effect of indium(III) as a central metal in in vitro and in vivo photosensitizing efficacy

The effects of an additional keto group on absorption wavelength and the corresponding metal complexes Zn(II), Cu(II) In(III) on singlet oxygen production and photodynamic efficacy were examined among the alkyl ether analogs of pyropheophorbide-a. For the preparation of the desired photosensitizers, the methyl 13(2)-oxo-pyropheophorbide-a obtained by reacting methyl pyropheophorbide-a with aqueous LiOH-THF was converted into a series of alkyl ether analogs. These compounds were evaluated for photophysical properties and in vitro (by means of the MTT assay and intracellular localization in RIF cells) and in vivo (in C3H mice implanted with RIF tumors) photosensitizing efficacy. Among the alkyl ether derivatives, the methyl 3-decyloxyethyl-3-devinyl-13(2)-oxo-pyropheophorbide-a was found to be most effective and the insertion of In(III) into this analog further enhanced its in vitro and in vivo photosensitizing efficacy. Fluorescence microscopy showed that, in contrast to the hexyl and dodecyl ether derivatives of HPPH (which localize in mitochondria and lysosomes, respectively), the diketo-analogs and their In(III) complexes localized in Golgi bodies. The preliminary in vitro and in vivo results suggest that, in both free-base and metalated analogs, the introduction of an additional keto group at the five-member exocyclic ring in pyropheophorbide-a diminishes its photosensitizing efficacy. This may be due to a shift in subcellular localization from mitochondria to the Golgi bodies. The further introduction of In(III) enhances photoactivity, but not by shifting the localization of the photosensitizer.     

Mononuclear to polynuclear transition induced by ligand coordination: synthesis, X-ray structure, and properties of mono-, di-, and polynuclear copper(II) complexes of pyridyl-containing azo ligands

Reactions of two hydrated cupric salts (CuCl(2).2H(2)O and Cu(ClO(4))(2).6H(2)O) with three azopyridyl ligands, viz. 2-[(arylamino)phenylazo]pyridine [aryl = phenyl (HL(1a)), p-tolyl (HL(1b)), and 2-thiomethyl phenyl (HL(1c))], 2-[2-(pyridylamino)phenylazo]pyridine (HL(2)), and 2-[3-(pyridylamino)phenylazo]pyridine (HL(3)), afford the mononuclear [CuClL(1)] (1), dinuclear [Cu(2)X(2)L(2)(2)](n)()(+) (X = Cl, H(2)O, ClO(4); n = 0, 1; 2, 3), and polynuclear [CuClL(3)](n)() (4) complexes, respectively, in high yields. Representative X-ray structures of these complexes 1-4 are reported. X-ray structure analysis of 4 reveals an infinite 1D zigzag chain that adopts a saw-tooth-like structure. Variable-temperature cryomagnetic measurements (2-300 K) on the complexes 2-4 have revealed weak magnetic interactions between the copper centers with J values -1.04, 9.88, and -1.31 cm(-1), respectively. Positive ion ESI mass spectra of the soluble complexes 1-3 are studied which provide the evidence for the integrity of the complexes also in solution. Visible range spectra of the complexes 1-3 in solution consist of intense and broad transitions in the range 700-600 nm. The solid-state spectrum of the insoluble copper complex 4, on the other hand, shows a structured band near 700 nm. The intensities of the transitions of the dinuclear complexes are much higher than those of the corresponding mononuclear copper complexes. Redox properties of the present copper complexes are reported. Notably, the dinuclear complex, 3, displays two successive redox processes: Cu(II)Cu(II) right harpoon over left harpoon Cu(II)Cu(I) right harpoon over left harpoon Cu(I)Cu(I). It catalyzes aerial oxidation of L-ascorbic acid. The catalytic cycle is most effective up to H(2)A/3 (H(2)A = L-ascorbic acid) molar ratio of 20:1.     

Characterization of porphyrins, chlorins, and bacteriochlorins formed via allomerization of bacteriochlorophyll a. Synthesis of highly stable bacteriopurpurinimides and their metal complexes

Allomerization of bacteriochlorophyll a (Bchl a) was studied under various reaction conditions. Bchl a on stirring with KOH/propanol produced an "unstable bacteriochlorin", which decomposed in acidic conditions to give a complex mixture containing bacteriopurpurin a as a principal component. The yields of other compounds varied and were found to be dependent on reaction condition. The structures of the isolated porphyrins, chlorins, and bacteriochlorins, related to Bchl a, were assigned on the basis of 1D, 2D NMR (ROESY), and mass spectroscopy analyses. The presence of fused anhydride rings in porphyrin, chlorin, and bacterichlorin systems showed a significant influence on their optical properties. Compared to bacteriochlorophyll a and bacteriopheophytin, the related structurally modified analogues, e.g., the bacteriopurpurin a, 13(1)/15(1)-N-alkyl isoimide, and the imide analogues were found to be more stable with a significant difference in spectroscopic properties. Bacteriochlorins containing anhydride, imide, or isoimide cyclic rings demonstrated a significant bathochromic shift of their Q bands in their electronic absorption spectra. Under basic conditions the formation of the 12-hydroxymethyl, 12-formyl, and 12-methylene analogues as byproducts from the 12-methyl-bacteriopurpurin-N-hexylimide could be due to subsequent oxidation of the vinylogous enolate intermediates. To investigate the effect of the central metal in the electronic spectra, the stable bacteriopurpurin-18-N-hexylimide was converted to a series of metal complexes [Zn(II), Cd(II), and Pd(II)] by following the direct or transmetalation approaches. Compared to the free-base analogue, these complexes showed a remarkable shift in their electronic absorption spectra.     

A mild and regioselective method for alpha-bromination of beta-keto esters and 1,3-diketones using bromodimethylsulfonium bromide (BDMS)

Bromodimethylsulfonium bromide has been found to be an effective and regioselective reagent for alpha-monobromination of beta-keto esters and 1,3-diketones. A wide variety of beta-keto esters and 1,3-diketones undergo chemoselective alpha-monobromination with excellent yields at 0-5 degrees C or room temperature. The notable advantages of this protocol are no need of chromatographic separation, use of less hazardous reagent than molecular bromine, and no added base, Lewis acid, or other catalyst.     

Conformally flat collapsing stars in <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>) gravity

The present work includes an analytical investigation of a collapsing spherical star in f(R) gravity. The interior of the collapsing star admits a conformal flatness. Information regarding the fate of the collapse is extracted from the matching conditions of the extrinsic curvature and the Ricci curvature scalar across the boundary hypersurface of the star. The radial distribution of the physical quantities such as density, anisotropic pressure and radial heat flux are studied. The inhomogeneity of the collapsing interior leads to a non-zero acceleration. The divergence of this acceleration and the loss of energy through a heat conduction forces the rate of the collapse to die down and the formation of a zero proper volume singularity is realized only asymptotically.