Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)

Effect of polyethylenimine, a cell permeabilizer, on the photosensitized destruction of algae by methylene blue and nuclear fast red

The present study reports the effect a cell permeabilizer, polyethylenimine (PEI) has on the photodynamic effect of methylene blue (MB) and nuclear fast red (NFR) in the presence of hydrogen peroxide (H₂O₂). The photosensitized destruction of the algae Chlorella vulgaris under irradiation with visible light is examined. The photodynamic effect was investigated under aerobic and anaerobic conditions. The presence of a permeabilizer during the photosensitized destruction of C. vulgaris does not enhance the activity of the MB, MB/H₂O₂ system or the NFR, NFR/H₂O ₂ system under aerobic conditions. However under anaerobic conditions we have determined that when a cell permeabilizer was added to the MB/H ₂O₂ system, the photosensitized destruction of C. vulgaris proceeded via a combination of Type I and Type II mechanisms. The presence of PEI enforces MB/H₂O₂ to be active toward the destruction of C. vulgaris whether oxygen is present or absent. Under aerobic and anaerobic conditions the activity of NFR was suppressed in the presence of PEI as a result of electrostatic interactions between the photosensitizer and the cell permeabilizer. The decrease in fluorescence recorded is indicative of destruction of the chlorophyll a pigment. 

Photosensitized destruction of Chlorella vulgaris by methylene blue or nuclear fast red combined with hydrogen peroxide under visible light irradiation

A considerable number of investigations have started to elucidate the essential roles biological agents play in the biodeterioration of stone. Chemical biocides are becoming increasingly banned because of the environmental and health hazards associated with these toxic substances. The present study reports the photodynamic effect of Methylene Blue (MB) and Nuclear Fast Red (NFR) in the presence of hydrogen peroxide (H₂O₂) on the destruction of the algae Chlorella vulgaris (C. vulgaris) under irradiation with visible light. Illumination of C. vulgaris in the presence of MB or NFR combined with H₂O₂ results in the decomposition of both the algal species and the photosensitizer. The photodynamic effect was investigated under aerobic and anaerobic conditions. Differences in mechanism type are reported and are dependent on both the presence and the absence of oxygen. The behavior of each photosensitizer leads to a Type II mechanism and a Type I/Type II combination for MB and NFR, respectively, being concluded. This novel combination could be effective for the remediation of biofilm-colonized stone surfaces.

Multiple major outbursts from a restless luminous blue variable in NGC 3432

We present new photometric and spectroscopic observations of an unusual luminous blue variable (LBV) in NGC 3432, covering three major outbursts in 2008 October, 2009 April and 2009 November. Previously, this star experienced an outburst also in 2000 (known as SN 2000ch). During outbursts the star reached an absolute magnitude between -12.1 and -12.8. Its spectrum showed H, He I and Fe II lines with P-Cygni profiles during and soon after the eruptive phases, while only intermediate-width lines in pure emission (including He II lambda 4686) were visible during quiescence. The fast-evolving light curve soon after the outbursts, the quasi-modulated light curve, the peak magnitude and the overall spectral properties are consistent with multiple episodes of variability of an extremely active LBV. However, the widths of the spectral lines indicate unusually high wind velocities (1500-2800 km s-1), similar to those observed in Wolf-Rayet stars. Although modulated light curves are typical of LBVs during the S-Dor variability phase, the luminous maxima and the high frequency of outbursts are unexpected in S-Dor variables. Such extreme variability may be associated with repeated ejection episodes during a giant eruption of an LBV. Alternatively, it may be indicative of a high level of instability shortly preceding the core-collapse or due to interaction with a massive, binary companion. In this context, the variable in NGC 3432 shares some similarities with the famous stellar system HD 5980 in the Small Magellanic Cloud, which includes an erupting LBV and an early Wolf-Rayet star.

Development and validation of a fast monoclonal based disequilibrium enzyme-linked immunosorbent assay for the detection of triphenylmethane dyes and their metabolites in fish

Malachite Green (MG), Crystal Violet (CV) and Brilliant Green (BC) are antibacterial, antifungal and antiparasitic agents that have been used for treatment and prevention of diseases in fish. These dyes are metabolized into reduced leuco forms (LMG, LCV, LBG) that can be present in fish muscles for a long period. Due to the carcinogenic properties they are banned for use in fish for human consumption in many countries including the European Union and the United States. HPLC and LC-MS techniques are generally used for the detection of these compounds and their metabolites in fish. This study presents the development of a fast enzyme-linked immunosorbent assay (ELISA) method as an alternative for screening purposes. A first monoclonal cell line producing antibodies to MG was generated using a hybridoma technique. The antibody had good cross-reactivates with related chromatic forms of triphenylmethane dyes such as CV, BC, Methyl Green, Methyl Violet and Victoria Blue R. The monoclonal antibody (mAb) was used to develop a fast (20 min) disequilibrium ELISA screening method for the detection of triphenylmethanes in fish. By introducing an oxidation step with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) during sample extraction the assay was also used to detect the presence of the reduced metabolites of triphenylmethanes. The detection capability of the assay was 1 ng g(-1) for MG, LMG, CV, LCV and BC which was below the minimum required performance limit (MRPL) for the detection method of total MG (sum of MG and LMG) set by the Commission Decision 2004/25/EC (2 ng g(-1)). The mean recoveries for fish samples spiked at 0.5 MRPL and MRPL levels with MG and LMG were between 74.9 and 117.0% and inter- and intra-assay coefficients of variation between 4.7 and 25.7%. The validated method allows the analysis of a batch of 20 samples in two to three hours. Additionally, this procedure is substantially faster than other ELISA methods developed for MG/LMG thus far. The stable and efficient monoclonal cell line obtained is an unlimited source of sensitive and specific antibody to MG and other triphenylmethanes. (C) 2011 Elsevier B.V. All rights reserved.

A Novel, Fast-Responding, Indicator Ink for Thin Film Photocatalytic Surfaces

A new photocatalyst indicator ink based on methylene blue (MB) is described that allows the presence and activity of a thin (15 nm) photocatalytic film to be assessed in seconds. The ink is very stable (shelf life > 6 months) and the color change (blue to colorless) striking. The ink utilizes a sacrificial electron donor, glycerol, to trap the photogenerated holes, leaving the photogenerated electrons to react with MB to produce its. reduced, leuco, form (LMB). The efficacy of the MB ink is due to the presence of acid in its formulation, which curtails significantly. the otherwise usual, rapid reoxidation of LMB by ambient O-2.

Correlation between the photocatalysed oxidation of methylene blue in solution and the reduction of resazurin in a photocatalyst activity indicator ink (Rz Paii)

Fast and frugal models of clinical judgement in novice and expert physicians

Our objective was to study whether “compensatory” models provide better descriptions of clinical judgment than fast and frugal models, according to expertise and experience. Fifty practitioners appraised 60 vignettes describing a child with an exacerbation of asthma and rated their propensities to admit the child. Linear logistic (LL) models of their judgments were compared with a matching heuristic (MH) model that searched available cues in order of importance for a critical value indicating an admission decision. There was a small difference between the 2 models in the proportion of patients allocated correctly (admit or not-admit decisions), 91.2% and 87.8%, respectively. The proportion allocated correctly by the LL model was lower for consultants than juniors, whereas the MH model performed equally well for both. In this vignette study, neither model provided any better description of judgments made by consultants or by pediatricians compared to other grades and specialties.