Electronic absorption and emission spectroscopic investigations of the interaction of the fullerenes, C60 and C70, with amines and aromatic molecules

Electronic absorption spectroscopy and fluorescence spectroscopy have been used to investigate the interaction of the fullerenes C60 and C70 with diethylaniline, and with aromatic solvents such as benzene. C60 interacts weakly with aromatic amines in the ground state while C70 does not interact at all. Steady state fluorescence emission and lifetime measurements show that both C60 and C70 form excited state complexes (exciplexes) with the amines in non-aromatic solvents such as methylcyclohexane, but not in benzene. In benzene, only fluorescence quenching is observed due to the interaction between the π systems of the aromatic solvent and the fullerene in the ground state. This is also borne out by the systematic study of solvent effects on the absorption and emission spectra of the fullerenes.

Phenotypic characters of rice landraces reveal independent lineages of short-grain aromatic indica rice

Rice landraces are lineages developed by farmers through artificial selection during the long-term domestication process. Despite huge potential for crop improvement, they are largely understudied in India. Here, we analyse a suite of phenotypic characters from large numbers of Indian landraces comprised of both aromatic and non-aromatic varieties. Our primary aim was to investigate the major determinants of diversity, the strength of segregation among aromatic and non-aromatic landraces as well as that within aromatic landraces. Using principal component analysis, we found that grain length, width and weight, panicle weight and leaf length have the most substantial contribution. Discriminant analysis can effectively distinguish the majority of aromatic from non-aromatic landraces. More interestingly, within aromatic landraces long-grain traditional Basmati and short-grain non-Basmati aromatics remain morphologically well differentiated. The present research emphasizes the general patterns of phenotypic diversity and finds out the most important characters. It also confirms the existence of very unique short-grain aromatic landraces, perhaps carrying signatures of independent origin of an additional aroma quantitative trait locus in the indica group, unlike introgression of specific alleles of the BADH2 gene from the japonica group as in Basmati. We presume that this parallel origin and evolution of aroma in short-grain indica landraces are linked to the long history of rice domestication that involved inheritance of several traits from Oryza nivara, in addition to O. rufipogon. We conclude with a note that the insights from the phenotypic analysis essentially comprise the first part, which will likely be validated with subsequent molecular analysis.

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

Savory peptides present in Moromi obtained from soy sauce fermentation of yellow soybean

The presence of savory peptides in moromi has been investigated. Moromi was prepared by fermenting yellow soybean using Aspergillus oryzae as the starter at the first step (mold fermentation) and 20% brine solution at the next step (brine fermentation). The moromi was then ultrafiltered stepwise using membranes with MW cut-offs of 10,000, 3,000, and 500 Da, respectively. The fraction with MW <500 Da was chromatographed using Sephadex G-25 SF to yield four fractions, 1-4. Analysis of soluble peptides, NaCl content, alpha-amino nitrogen, amino acid composition, peptide profile using CE coupled with DAD, taste profile and free glutamic acid content, were performed for each fraction. Fraction 2 contained a relatively high total glutamic acid content, but a relatively low free glutamic acid content and had the highest umami taste. This fraction also had more peptides containing non-aromatic amino acids than the other fractions. The peptides present in fraction 2 may play a role, at least in part, in its intense umami taste.

Phagocytic and serum killing of capsulate and non-capsulate Bacteroides fragilis

The relative susceptibilities of capsulate and non- capsulate variants of Bacteroides fragilis to serum and phagocytic killing were investigated. The capsule of B. fragilis did not confer resistance to serum killing. Phagocytic killing of non- capsulate B. fragilis occurred at bacterial concentrations of 1 X 10(6) and 1 X 10(7) cfu/ml. Capsulate B. fragilis organisms were also phagocytosed and killed at a concentration of 1 X 10(6) cfu/ml, but phagocytosis and killing were impaired at a concentration of 1 X 10(7) cfu/ml.

Mesure du rapport d'embranchement des désintégrations B^0--> pi^- l^+v et B^+--> êta^(') l^+v, du spectre des facteurs de forme des désintégrations B^0--> pi^- l^+v et B^+--> êta l^+v, et extraction de |V_ub| dans l'expérience BABAR

Nous rapportons les résultats d'une étude des désintégrations semileptoniques non-charmées B^+--> êta^(') l^+v et B^0--> pi^- l^+v, mesurés par le détecteur BABAR avec une production d'environ 464 millions de paires de mésons BBbar issues des collisions e^+e^- à la résonance Upsilon(4S). L'analyse reconstruit les événements avec une technique relâchée des neutrinos. Nous obtenons les rapports d'embranchement partiels pour les désintégrations B^+--> êta l^+v et B^0--> pi^- l^+v en trois et douze intervalles de q^2, respectivement, à partir desquels nous extrayons les facteurs de forme f_+(q^2) et les rapports d'embranchement totaux B(B^+--> êta l^+v) = (3.39 +/- 0.46_stat +/- 0.47_syst) x 10^-5 et B(B^0--> pi^- l^+v) = (1.42 +/- 0.05_stat +/- 0.08_syst) x 10^-4. Nous mesurons aussi B(B^+--> êta' l^+v) = (2.43 +/- 0.80_stat +/- 0.34_syst) x 10^-5. Nous obtenons les valeurs de la norme de l'élément |V_ub| de la matrice CKM en utilisant trois calculs différents de la CDQ.

Savory peptides present in Moromi obtained from soy sauce fermentation of yellow soybean

The presence of savory peptides in moromi has been investigated. Moromi was prepared by fermenting yellow soybean using Aspergillus oryzae as the starter at the first step (mold fermentation) and 20% brine solution at the next step (brine fermentation). The moromi was then ultrafiltered stepwise using membranes with MW cut-offs of 10,000, 3,000, and 500 Da, respectively. The fraction with MW < 500 Da was chromatographed using Sephadex G-25 SF to yield four fractions, 1-4. Analysis of soluble peptides, NaCl content, alpha-amino nitrogen, amino acid composition, peptide profile using CE coupled with DAD, taste profile and free glutamic acid content, were performed for each fraction. Fraction 2 contained a relatively high total glutamic acid content, but a relatively low free glutamic acid content and had the highest umami taste. This fraction also had more peptides containing non-aromatic amino acids than the other fractions. The peptides present in fraction 2 may play a role, at least in part, in its intense umami taste.

Ligand effects in cis-Ru-II(N-N)(2)L-2 species where N-N is a substituted 2,2 '-bisoxazoline and L is monodentate

Starting from previously reported cis-Ru(MeL)(2)Cl-2, where MeL is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, cis-Ru(MeL)(2)Br-2 (1), cis-Ru( MeL)(2)I-2 (2), cis-Ru(MeL)(2)(NCS)(2) center dot H2O (3), cis-Ru(MeL)(2)(N-3)(2) (4) and cis-[Ru(MeL)(2)(MeCN)(2)](PF6)(2) center dot (CH3)(2)CO (5) are synthesised. The X-ray crystal structures of complexes 1, 2, 3 and 5 have been determined. All the five new complexes have been characterized by FTIR, ESIMS and H-1 NMR. In cyclic voltammetry in acetonitrile at a glassy carbon electrode, the complexes display a quasireversible Ru(II/III) couple in the range 0.32-1.71 V versus NHE. The Ru(II/III) potentials yield a satisfactorily linear correlation with Chatt's ligand constants P-L for the monodantate ligands. From the intercept and by comparing the known situation in Ru(2,2'-bipyridine)(2)L-2, it is concluded that MeL, a non-aromatic diimine, is significantly more pi-acidic than 2,2'-bipyridine. (c) 2008 Elsevier B.V. All rights reserved.

Flavonoid inhibitory pharmacodynamics on platelet function in physiological environments

The complex relationship between flavonoid-based nutrition and cardiovascular disease may be dissected by understanding the activities of these compounds in biological systems. The aim of the present study was to explore a hierarchy for the importance of dietary flavonoids on cardiovascular health by examining the structural basis for inhibitory effects of common, dietary flavonoids (quercetin, apigenin, and naringenin) and the plasma metabolite, tamarixetin. Understanding flavonoid effects on platelets in vivo can be informed by investigations of the ability of these compounds to attenuate the function of these cells. Inhibition of platelet function in whole blood and plasma was structure-dependent. The order of potency was apigenin > tamarixetin > quercetin = naringenin indicating that in vivo, important functional groups are potentially a methylated B ring, and a non-hydroxylated, planar C ring. Apigenin and the methylated metabolite of quercetin, tamarixetin significantly reduced thrombus volume at concentrations (5 μM) that suggested their reported physiological levels (0.1-1 μM) may exert low levels of inhibition. Flavonoid interactions with erythrocytes, leukocytes and human serum albumin in whole blood reduce their inhibitory activities against platelet function. The diminished inhibitory activity of flavonoids that we observed in whole blood and plasma indicated that these interactions do not overcome the attenuating effects of these compounds. Furthermore, inhibition of platelet aggregation by flavonoids was enhanced with increases in exposure time, indicating the potential for measurable inhibitory effects during resident plasma times. We conclude that flavonoid structures may be a major influence of their activities in vivo with methylated metabolites and those of flavones being more potent than those of flavonols and flavanones.

Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Reactive power dispatch and planning using a non-linear branch-and-bound algorithm

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Unconstrained variables of non-commutative open strings

The boundary conditions of the bosonic string theory in non-zero B-field background are equivalent to the second class constraints of a discretized version of the theory. By projecting the original canonical coordinates onto the constraint surface we derive a set of coordinates of string that are unconstrained. These coordinates represent a natural framework for the quantization of the theory.

Prompt and non-prompt J/ψ production in pp collisions at √s =7 TeV

The production of J/ψ mesons is studied in pp collisions at √s = 7 TeV with the CMS experiment at the LHC. The measurement is based on a dimuon sample corresponding to an integrated luminosity of 314 nb-1. The J/ψ differential cross section is determined, as a function of the J/ψ transverse momentum, in three rapidity ranges. A fit to the decay length distribution is used to separate the prompt from the non-prompt (b hadron to J/ψ) component. Integrated over J/ψ transverse momentum from 6.5 to 30 GeV/c and over rapidity in the range {pipe}y{pipe} < 2.4, the measured cross sections, times the dimuon decay branching fraction, are 70.9 ± 2.1(stat.) ± 3.0(syst.) ± 7.8(luminosity) nb for prompt J/ψ mesons assuming unpolarized production and 26.0 ± 1.4(stat.) ± 1.6(syst.) ± 2.9(luminosity) nb for J/ψ mesons from b-hadron decays. © CERN for the benefit of the CMS collaboration 2011.

Dynamical twisting and the b ghost in the pure spinor formalism

After adding an RNS-like fermionic vector ψ m to the pure spinor formalism, the non-minimal b ghost takes a simple form similar to the pure spinor BRST operator. The N=2 superconformal field theory generated by the b ghost and the BRST current can be interpreted as a dynamical twisting of the RNS formalism where the choice of which spin 1/2 ψ m variables are twisted into spin 0 and spin 1 variables is determined by the pure spinor variables that parameterize the coset SO(10)/U(5). © 2013 SISSA, Trieste, Italy.