Study on adsorption and oxidation of calf thymus DNA at glassy carbon electrode

The oxidation and adsorption of the temperature-denatured DNA at GC electrode are studied by differential pulse voltammetry and in situ FTIR spectroelectrochemistry. The temperature-denatured DNA is adsorbed and formed a DNA multilayer at electrode surface. The temperature-denatured DNA showing partly reversible process was first observed based on the reduction peaks appearing at negative scans and the reversible spectral change. The oxidation product of the temperature-denatured DNA can not diffuse away from the electrode surface easily due to the impediment of the DNA multilayer, so it can be partly reduced.

Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.

Indole ring oxidation by activated leukocytes prevents the production of hypochlorous acid

Hypochlorous acid (HOCl) released by activated leukocytes has been implicated in the tissue damage that characterizes chronic inflammatory diseases. In this investigation, 14 indole derivatives, including metabolites such as melatonin, tryptophan and indole-3-acetic acid, were screened for their ability to inhibit the generation of this endogenous oxidant by stimulated leukocytes. The release of HOCl was measured by the production of taurine-chloramine when the leukocytes (2 x 10(6) cells/mL) were incubated at 37ºC in 10 mM phosphate-buffered saline, pH 7.4, for 30 min with 5 mM taurine and stimulated with 100 nM phorbol-12-myristate acetate. Irrespective of the group substituted in the indole ring, all the compounds tested including indole, 2-methylindole, 3-methylindole, 2,3-dimethylindole, 2,5-dimethylindole, 2-phenylindole, 5-methoxyindole, 6-methoxyindole, 5-methoxy-2-methylindole, melatonin, tryptophan, indole-3-acetic acid, 5-methoxy-2-methyl-3-indole-acetic acid, and indomethacin (10 µM) inhibited the chlorinating activity of myeloperoxidase (MPO) in the 23-72% range. The compounds 3-methylindole and indole-3-acetic acid were chosen as representative of indole derivatives in a dose-response study using purified MPO. The IC50 obtained were 0.10 ± 0.03 and 5.0 ± 1.0 µM (N = 13), respectively. These compounds did not affect the peroxidation activity of MPO or the production of superoxide anion by stimulated leukocytes. By following the spectral change of MPO during the enzyme turnover, the inhibition of HOCl production can be explained on the basis of the accumulation of the redox form compound-II (MPO-II), which is an inactive chlorinating species. These results show that indole derivatives are effective and selective inhibitors of MPO-chlorinating activity.

Estudo das propriedades dosimétricas de polímeros conjugados

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.

PRIM: Proximity imaging of green fluorescent protein-tagged polypeptides

We report a serendipitous discovery that extends the impressive catalog of reporter functions performed by green fluorescent protein (GFP) or its derivatives. When two GFP molecules are brought into proximity, changes in the relative intensities of green fluorescence emitted upon excitation at 395 vs. 475 nm result. These spectral changes provide a sensitive ratiometric index of the extent of self-association that can be exploited to quantitatively image homo-oligomerization or clustering processes of GFP-tagged proteins in vivo. The method, which we term proximity imaging (PRIM), complements fluorescence resonance energy transfer between a blue fluorescent protein donor and a GFP acceptor, a powerful method for imaging proximity relationships between different proteins. However, unlike fluorescence resonance energy transfer (which is a spectral interaction), PRIM depends on direct contact between two GFP modules, which can lead to structural perturbations and concomitant spectral changes within a module. Moreover, the precise spatial arrangement of the GFP molecules within a given dimer determines the magnitude and direction of the spectral change. We have used PRIM to detect FK1012-induced dimerization of GFP fused to FK506-binding protein and clustering of glycosylphosphatidylinositol-anchored GFP at cell surfaces.

In vitro assembly of phytochrome B apoprotein with synthetic analogs of the phytochrome chromophore

Phytochrome B (PhyB), one of the major photosensory chromoproteins in plants, mediates a variety of light-responsive developmental processes in a photoreversible manner. To analyze the structural requirements of the chromophore for the spectral properties of PhyB, we have designed and chemically synthesized 20 analogs of the linear tetrapyrrole (bilin) chromophore and reconstituted them with PhyB apoprotein (PHYB). The A-ring acts mainly as the anchor for ligation to PHYB, because the modification of the side chains at the C2 and C3 positions did not significantly influence the formation or difference spectra of adducts. In contrast, the side chains of the B- and C-rings are crucial to position the chromophore properly in the chromophore pocket of PHYB and for photoreversible spectral changes. The side-chain structure of the D-ring is required for the photoreversible spectral change of the adducts. When methyl and ethyl groups at the C17 and C18 positions are replaced with an n-propyl, n-pentyl, or n-octyl group, respectively, the photoreversible spectral change of the adducts depends on the length of the side chains. From these studies, we conclude that each pyrrole ring of the linear tetrapyrrole chromophore plays a different role in chromophore assembly and the photochromic properties of PhyB.

Optimization and characterization of femtosecond laser inscribed in-fiber microchannels for liquid sensing

In-fiber microchannels were fabricated directly in standard single mode fiber using the femtosecond laser inscribe and etch technique. This method of creating in-fiber microchannels offers great versatility since it allows complex three dimensional structures to be inscribed and then etched with hydrofluoric acid. Four in-fiber microchannel designs were experimentally investigated using this technique. Device characteristics were evaluated through monitoring the spectral change while inserting index matching oils into each microchannel - a R.I. sensitivity up to 1.55 dB/RIU was achieved. Furthermore, a simple Fabry-Pérot based refractometer with a R.I. sensitivity of 2.75 nm/RIU was also demonstrated. © 2014 SPIE.

Optimization and characterization of femtosecond laser inscribed in-fiber microchannels for liquid sensing

In-fiber microchannels were fabricated directly in standard single mode fiber using the femtosecond laser inscribe and etch technique. This method of creating in-fiber microchannels offers great versatility, since it allows complex three-dimensional structures to be inscribed and then preferentially etched with hydrofluoric acid. In addition, inscription does not require a photosensitive fiber; the modification is induced through nonlinear processes triggered by an ultrashort laser pulse. Four in-fiber microchannel designs were experimentally investigated using this technique - microhole, microslot channel along the core, microslot channel perpendicular to the core and helical channel around the core. Each device design was evaluated through monitoring the optical spectral change while inserting a range of index matching oils into each microchannel; an R.I. sensitivity up to 1.55 dB/RIU was achieved in these initial tests. Furthermore, an all femtosecond laser inscribed Fabry-Pérot-based refractometer with an R.I. sensitivity of 2.75 nm/RIU was also demonstrated. The Fabry-Pérot refractometer was formed by positioning a microchannel between two femtosecond laser inscribed point-by-point fiber Bragg gratings.

Silk fibroin as a water-soluble bio-resist and its thermal properties

Thermal diffusivity of silk fibroin films, α = (1.6 ± 0.24) × 10-7 m2 s-1, was measured by a direct contact method. It was shown to be reduced down to ∼1 × 10-7 m2 s-1 in the crystallized phase, consistent with the multi-domain composition of β-sheet assemblies. Crystalline silk with β-sheets was made by dipping into alcohol and was used as a positive electron beam lithography (EBL) resist. It is shown by direct IR imaging of the 1619 cm-1 amide-I CO spectral signature and 3290 cm-1 amide-A N-H stretching band that an e-beam is responsible for unzipping β-sheets, which subsequently results in exposed areas returning to a water soluble state. This makes it possible to develop a water-based biocompatible silk resist and use it in lithography applications. The general principles of protein crystallization, traceable to spectral changes in IR amide bands of silk, can be used as a guide for the creation of new protein EBL resists and to quantify the electron dose required for solubility. Foam formation and laser treatments of silk can provide new approaches in surface functionalization and fabrication of 3D bio-scaffolds.

THE VALENCE CHANGE FROM RE3+ TO RE2+ (RE-EQUIVALENT-TO-EU, SM, YB) IN SRB4O7-RE PREPARED IN AIR AND THE SPECTRAL PROPERTIES OF RE2+

A valence change from RE3+ to RE2+ (RE=Eu, Sm, Yb) was observed in samples of SrB4O7: RE prepared by solid state reaction at high temperature in air. The phosphors SrB4O7: RE2+ show efficient luminescence at room temperature. The broad band d-f emissions of Eu2+ and Yb2+ are at 367 and 360 nm respectively. The sharp line f-f emissions of the Sm2+ ion (5D0-F-7(J)) are in the range 680-780 nm. The probable reasons for the valence change of Eu, Sm and Yb in this host are discussed.

Palaeoclimate change recorded in Upper Cretaceous (Albian-Cenomanian) Kazhdumi Formation Borehole spectral Gamma-Ray Logs, South Pars Gas field, Persian Gulf

Th/U and Th/K data from spectral gamma-ray logs obtained from outcrop successions have been used as a rapid and inexpensive proxy for determining possible episodes of humid-arid palaeoclimate change. Such outcrop-based measurements have never been tested using spectral gamma-ray data obtained from wireline logs in subsurface boreholes. Th/K and Th/U ratios have traditionally been used to decipher sequence stratigraphic patterns, at outcrop and in borehole. The possible influence of palaeoclimate on such ratio changes has yet to be proven, especially from borehole data. In this work, we compare borehole-derived Th/K (and to a lesser extent Th/U) to palaeoenvironmental changes inferred from palynology and deduce that both sea level and changing hinterland weathering regimes caused discrete fluctuations observed in the spectral gamma-ray logs. This is the first time such subsurface information has been used in this way. Interpretation of wireline logs in terms of palaeoclimate as well as sea level may now be considered, and the use of such logs in palaeoclimate reconstruction is strengthened.