Polymethine cyanine dyes in beta-cyclodextrin solution: multiple equilibria and chemical oxidation

Absorption and fluorescence spectroscopy, electrochemical techniques, and semiempirical calculations were employed to characterize the multiple complexation equilibria between two polymethine cyanine dyes (IR-786 and Indocyanine green-ICG, 5) and beta-cyclodextrin (beta-CD, L), as well as the chemical reactivity of the complexed and uncomplexed species against the oxidizing agents hypochlorite (HC) and hydrogen peroxide (HP). IR-786 dimerization is favored with the increase in beta-CD concentration in the form of (SL)(2) complexes. In the case of ICG, free dimers (D) and SL complexes are favored. Both IR-786 and ICG react and discolor in the presence of HC and HP. For IR-786, the reaction with HP and HC proceeds with observed rate constants of 10(-3) and 0.28 s(-1) and second-order rate constants (k(2)) of similar to 10(-3) and 10(4) M(-1) s(-1), respectively. The intermediate species observed in the bleaching reactions of IR-786 and ICG were shown, by cyclic voltammetry and VIS absorption, to result from one electron oxidation. IR-786 complexed with beta-CD is protected against bleaching in the presence of HP and HC by factors of 20 and 4, respectively. This protection was not observed in ICG complexes. Superdelocalizability profile of both dyes and frontier orbital analysis indicates that beta-CD does not protect ICG from oxidation by HP or HC, whereas the 2:2 IR-786/beta-Cd complex is able to avoid the oxidation of IR-786. We concluded that the decrease in the chemical reactivity of the dyes against oxidant agents in the presence of beta-CD is due to the formation of (SL)(2) complexes. Copyright (C) 2010 John Wiley & Sons, Ltd.

Ligand dissociation from estrogen receptor is mediated by receptor dimerization: Evidence from molecular dynamics simulations

Estrogen Receptor (ER) is an important target for pharmaceutical design. Like other ligand-dependent transcription factors, hormone binding regulates ER transcriptional activity. Nevertheless, the mechanisms by which ligands enter and leave ERs and other nuclear receptors remain poorly understood. Here, we report results of locally enhanced sampling molecular dynamics simulations to identify dissociation pathways of two ER ligands [the natural hormone 17 beta-estradiol (E-2) and the selective ER modulator raloxifene (RAL)] from the human ER alpha ligand-binding domain in monomeric and dimeric forms. E-2 dissociation occurs via three different pathways in ER monomers. One resembles the mousetrap mechanism (Path I), involving repositioning of helix 12 (H12), others involve the separation of H8 and H11 (Path II), and a variant of this pathway at the bottom of the ligand-binding domain (Path II`). RAL leaves the receptor through Path I and a Path I variant in which the ligand leaves the receptor through the loop region between H11 and H12 (Path I`). Remarkably, ER dimerization strongly suppresses Paths II and II` for E-2 dissociation and modifies RAL escape routes. We propose that differences in ligand release pathways detected in the simulations for ER monomers and dimers provide an explanation for previously observed effects of ER quaternary state on ligand dissociation rates and suggest that dimerization may play an important, and hitherto unexpected, role in regulation of ligand dissociation rates throughout the nuclear receptor family.

Enhanced bone apposition to Brazilian microrough titanium surfaces

It has recently been reported that machined and microrough (micro) Brazilian titanium (Ti) implants have good production standards. The aim of this study was to evaluate in vivo bone formation around 2 different implant surfaces placed in dog's mandible. Thirty-two screw-typed Ti implants were used in this study. Mandibular premolars were extracted in 8 dogs and, after 12 weeks, 2 machined (Neodent Titamax, Brazil) and 2 micro implants (Neodent Titamax Porous, Brazil) were placed in each animal. Biopsies were taken at 3 and 8 weeks post-implantation and stained with Stevenel's blue and Alizarin red for histomorphometric measurements of bone-to-implant contact (BIC), bone area between threads (BABT) and bone area within the mirror area (BAMA). Data were analyzed statistically by two-way ANOVA (α=0.05). While at 3 weeks micro implants exhibited significantly more BIC than machined ones (55 ± 12.5% and 35.6 ± 15%, p<0.05), no significant difference in such parameter was detected at 8 weeks (51.2 ± 21% and 48.6 ± 18.1%, p>0.05). There were no significant differences in BABT and BAMA between the implants. Micro surfaces promoted higher contact osteogenesis. These data indicate that this commercial micro Ti implant surface enhances contact osteogenesis at an early post-implantation period when compared to the machined one.

Enhanced response of the fricke solution doped with hematoporphyrin under X-rays irradiation

The vials filled with Fricke solutions were doped with increasing concentrations of Photogem®, used in photodynamic therapy. These vials were then irradiated with low-energy X-rays with doses ranging from 5 to 20 Gy. The conventional Fricke solution was also irradiated with the same doses. The concentration of ferric ions for the Fricke and doped-Fricke irradiated solutions were measured in a spectrophotometer at 220 to 340 nm. The results showed that there was an enhancement in the response of the doped-Fricke solution, which was proportional to the concentration of the photosensitizer. The use of such procedure for studying the radiosensitizing property of photosensitizers based on the production of free radicals is also discussed.

Enhanced luminescence of Tb(3+)/Eu(3+) doped tellurium oxide glass containing silver nanostructures

We report on energy transfer studies in terbium (Tb(3+))-europium (Eu(3+)) doped TeO(2)-ZnO-Na(2)O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approximate to 480 to approximate to 700 nm. Enhanced Eu(3+) luminescence at approximate to 590 nm (transition (5)D(0)-(7)F(1)) and approximate to 614 nm (transition (5)D(0)-(7)F(2)) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb(3+)-Eu(3+) energy transfer and the contribution of the intensified local field on the Eu(3+) ions located near silver nanostructures.

Surface-plasmon-enhanced frequency upconversion in Pr(3+) doped tellurium-oxide glasses containing silver nanoparticles

A frequency upconversion process in Pr(3+) doped TeO(2)-ZnO glasses containing silver nanoparticles is studied under excitation with a nanosecond laser operating at 590 nm, in resonance with the (3)H(4)-->(1)D(2) transition. The excited Pr(3+) ions exchange energy in the presence of the nanoparticles, originating efficient conversion from orange to blue. The enhancement in the intensity of the luminescence at similar to 482 nm, corresponding to the (3)P(0)-->(3)H(4) transition, is due to the influence of the large local field on the Pr(3+) ions, which are located near the metallic nanoparticles. (C) 2008 American Institute of Physics.

Enhanced strange baryon production in Au+Au collisions compared to p+p at root s(NN)=200 GeV

We report on the observed differences in production rates of strange and multistrange baryons in Au+Au collisions at s(NN)=200 GeV compared to p+p interactions at the same energy. The strange baryon yields in Au+Au collisions, when scaled down by the number of participating nucleons, are enhanced relative to those measured in p+p reactions. The enhancement observed increases with the strangeness content of the baryon, and it increases for all strange baryons with collision centrality. The enhancement is qualitatively similar to that observed at the lower collision energy s(NN)=17.3 GeV. The previous observations are for the bulk production, while at intermediate p(T),1 < p(T)< 4 GeV/c, the strange baryons even exceed binary scaling from p+p yields.

[O/Fe] ESTIMATES FOR CARBON-ENHANCED METAL-POOR STARS FROM NEAR-INFRARED SPECTROSCOPY

We report on oxygen abundances determined from medium-resolution near-infrared spectroscopy for a sample of 57 carbon-enhanced metal-poor (CEMP) stars selected from the Hamburg/ESO Survey. The majority of our program stars exhibit oxygen-to-iron ratios in the range +0.5 < [O/Fe]< + 2.0. The [O/Fe] values for this sample are statistically compared to available high-resolution estimates for known CEMP stars as well as to high-resolution estimates for a set of carbon-normal metal-poor stars. Carbon, nitrogen, and oxygen abundance patterns for a sub-sample of these stars are compared to yield predictions for very metal-poor asymptotic giant branch (AGB) abundances in the recent literature. We find that the majority of our sample exhibit patterns that are consistent with previously studied CEMP stars having s-process-element enhancements and thus have very likely been polluted by carbon- and oxygen-enhanced material transferred from a metal-poor AGB companion.

A SEARCH FOR UNRECOGNIZED CARBON-ENHANCED METAL-POOR STARS IN THE GALAXY

We have developed a new procedure to search for carbon-enhanced metal-poor (CEMP) stars from the Hamburg/ESO (HES) prism-survey plates. This method employs an extended line index for the CH G band, which we demonstrate to have superior performance when compared to the narrower G-band index formerly employed to estimate G-band strengths for these spectra. Although CEMP stars have been found previously among candidate metal-poor stars selected from the HES, the selection on metallicity undersamples the population of intermediate-metallicity CEMP stars (-2.5 <= [Fe/H] <= -1.0); such stars are of importance for constraining the onset of the s-process in metal-deficient asymptotic giant branch stars (thought to be associated with the origin of carbon for roughly 80% of CEMP stars). The new candidates also include substantial numbers of warmer carbon-enhanced stars, which were missed in previous HES searches for carbon stars due to selection criteria that emphasized cooler stars. A first subsample, biased toward brighter stars (B < 15.5), has been extracted from the scanned HES plates. After visual inspection (to eliminate spectra compromised by plate defects, overlapping spectra, etc., and to carry out rough spectral classifications), a list of 669 previously unidentified candidate CEMP stars was compiled. Follow-up spectroscopy for a pilot sample of 132 candidates was obtained with the Goodman spectrograph on the SOAR 4.1 m telescope. Our results show that most of the observed stars lie in the targeted metallicity range, and possess prominent carbon absorption features at 4300 angstrom. The success rate for the identification of new CEMP stars is 43% (13 out of 30) for [Fe/H] < -2.0. For stars with [Fe/H] < -2.5, the ratio increases to 80% (four out of five objects), including one star with [Fe/H] < -3.0.

Enhanced Production of Direct Photons in Au plus Au Collisions at root s(NN)=200 GeV and Implications for the Initial Temperature

The production of e(+)e(-) pairs for m(e+e-) < 0.3 GeV/c(2) and 1< p(T) < 5 GeV/c is measured in p + p and Au + Au collisions at root s(NN) = 200 GeV. An enhanced yield above hadronic sources is observed. Treating the excess as photon internal conversions, the invariant yield of direct photons is deduced. In central Au + Au collisions, the excess of the direct photon yield over p + p is exponential in transverse momentum, with an inverse slope T = 221 +/- 19(stat) +/- 19(syst) MeV. Hydrodynamical models with initial temperatures ranging from T(init) similar to 300-600 MeV at times of similar to 0.6-0.15 fm/c after the collision are in qualitative agreement with the data. Lattice QCD predicts a phase transition to quark gluon plasma at similar to 170 MeV.

High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Chromic materials for responsive surface-enhanced resonance Raman scattering systems: a nanometric pH sensor

The use of chromic materials for responsive surface-enhanced resonance Raman scattering (SERRS) based nanosensors is reported. The potential of nano-chromic SERRS is demonstrated with the use of the halochrome methyl yellow to fabricate an ultrasensitive pH optical sensor. Some of the challenges of the incorporation of chromic materials with metal nanostructures are addressed through the use of computational calculations and a comparison to measured SERRS and surface-enhanced Raman scattering (SERS) spectra is presented. A strong correlation between the measured SERRS and the medium's proton concentration is demonstrated for the pH range 2-6. The high sensitivity achieved by the use of resonance Raman conditions is shown through responsive SERRS measurements from only femtolitres of volume and with the concentration of the reporting molecules approaching the single molecule regime.

Enhanced aeroelastic energy harvesting by exploiting combined nonlinearities: theory and experiment

Converting aeroelastic vibrations into electricity for low power generation has received growing attention over the past few years. In addition to potential applications for aerospace structures, the goal is to develop alternative and scalable configurations for wind energy harvesting to use in wireless electronic systems. This paper presents modeling and experiments of aeroelastic energy harvesting using piezoelectric transduction with a focus on exploiting combined nonlinearities. An airfoil with plunge and pitch degrees of freedom (DOF) is investigated. Piezoelectric coupling is introduced to the plunge DOF while nonlinearities are introduced through the pitch DOF. A state-space model is presented and employed for the simulations of the piezoaeroelastic generator. A two-state approximation to Theodorsen aerodynamics is used in order to determine the unsteady aerodynamic loads. Three case studies are presented. First the interaction between piezoelectric power generation and linear aeroelastic behavior of a typical section is investigated for a set of resistive loads. Model predictions are compared to experimental data obtained from the wind tunnel tests at the flutter boundary. In the second case study, free play nonlinearity is added to the pitch DOF and it is shown that nonlinear limit-cycle oscillations can be obtained not only above but also below the linear flutter speed. The experimental results are successfully predicted by the model simulations. Finally, the combination of cubic hardening stiffness and free play nonlinearities is considered in the pitch DOF. The nonlinear piezoaeroelastic response is investigated for different values of the nonlinear-to-linear stiffness ratio. The free play nonlinearity reduces the cut-in speed while the hardening stiffness helps in obtaining persistent oscillations of acceptable amplitude over a wider range of airflow speeds. Such nonlinearities can be introduced to aeroelastic energy harvesters (exploiting piezoelectric or other transduction mechanisms) for performance enhancement.

Phase Equilibrium and Optimization Tools: Application for Enhanced Structured Lipids for Foods

Solid-liquid phase equilibrium modeling of triacylglycerol mixtures is essential for lipids design. Considering the alpha polymorphism and liquid phase as ideal, the Margules 2-suffix excess Gibbs energy model with predictive binary parameter correlations describes the non ideal beta and beta` solid polymorphs. Solving by direct optimization of the Gibbs free energy enables one to predict from a bulk mixture composition the phases composition at a given temperature and thus the SFC curve, the melting profile and the Differential Scanning Calorimetry (DSC) curve that are related to end-user lipid properties. Phase diagram, SFC and DSC curve experimental data are qualitatively and quantitatively well predicted for the binary mixture 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1,2,3-tripalmitoyl-sn-glycerol (PPP), the ternary mixture 1,3-dimyristoyl-2-palmitoyl-sn-glycerol (MPM), 1,2-distearoyl-3-oleoyl-sn-glycerol (SSO) and 1,2,3-trioleoyl-sn-glycerol (OOO), for palm oil and cocoa butter. Then, addition to palm oil of Medium-Long-Medium type structured lipids is evaluated, using caprylic acid as medium chain and long chain fatty acids (EPA-eicosapentaenoic acid, DHA-docosahexaenoic acid, gamma-linolenic-octadecatrienoic acid and AA-arachidonic acid), as sn-2 substitutes. EPA, DHA and AA increase the melting range on both the fusion and crystallization side. gamma-linolenic shifts the melting range upwards. This predictive tool is useful for the pre-screening of lipids matching desired properties set a priori.

Vibration-enhanced posture stabilization achieved by tactile supplementation: May blind individuals get extra benefits?

Diminished balance ability poses a serious health risk due to the increased likelihood of falling, and impaired postural stability is significantly associated with blindness and poor vision. Noise stimulation (by improving the detection of sub-threshold somatosensory information) and tactile supplementation (i.e. additional haptic information provided by an external contact surface) have been shown to improve the performance of the postural control system. Moreover, vibratory noise added to the source of tactile supplementation (e.g. applied to a surface that the fingertip touches) has been shown to enhance balance stability more effectively than tactile supplementation alone. In view of the above findings, in addition to the well established consensus that blind subjects show superior abilities in the use of tactile information, we hypothesized that blind subjects may take extra benefits from the vibratory noise added to the tactile supplementation and hence show greater improvements in postural stability than those observed for sighted subjects. If confirmed, this hypothesis may lay the foundation for the development of noise-based assistive devices (e.g. canes, walking sticks) for improving somatosensation and hence prevent falls in blind individuals. (C) 2011 Elsevier Ltd. All rights reserved.