Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Synthesis of electrically conducting copolymers of o-/m-toluidines and o-/m-amino benzoic acid in an organic peroxide system and their characterization

Copolymers of o-lm-toluidine with o-lm-amino benzoic acid have been synthesized by chemical polymerization using inverse emulsion pathway and characterized by a number of techniques including UV-Vis, FT-IR, FT Raman, EPR and NMR spectroscopies, thermal analysis and conductivity. The solubility of the copolymers in organic solvents increases with increase in the amount of amino benzoic acid in the feed. The copolymers synthesized at room temperature show relatively higher conductivity and are obtained in higher yield compared to those synthesized at 0 and 60 degreesC. The spectral studies have revealed restricted conjugation along the polymer chain. The effect of -COOH substituent on the copolymer structure is discussed. (C) 2003 Elsevier Science B.V All rights reserved.

A Modified Fluorimetric Method for Determination of Hydrogen Peroxide Using Homovanillic Acid Oxidation Principle

Hydrogen peroxide (H2O2) level in biological samples is used as an important index in various studies. Quantification of H2O2 level in tissue fractions in presence of H2O2 metabolizing enzymes may always provide an incorrect result. A modification is proposed for the spectrofluorimetric determination of H2O2 in homovanillic acid (HVA) oxidation method. The modification was included to precipitate biological samples with cold trichloroacetic acid (TCA, 5% w/v) followed by its neutralization with K2HPO4 before the fluorimetric estimation of H2O2 is performed. TCA was used to precipitate the protein portions contained in the tissue fractions. After employing the above modification, it was observed that H2O2 content in tissue samples was >= 2 fold higher than the content observed in unmodified method. Minimum 2 h incubation of samples in reaction mixture was required for completion of the reaction. The stability of the HVA dimer as reaction product was found to be > 12 h. The method was validated by using known concentrations of H2O2 and catalase enzyme that quenches H2O2 as substrate. This method can be used efficiently to determine more accurate tissue H2O2 level without using internal standard and multiple samples can be processed at a time with additional low cost reagents such as TCA and K2HPO4.

Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing

Manganese dioxide nanoparticles were synthesized by chemical reduction route at different growth temperatures of 40 degrees C, 80 degrees C, 100 degrees C and were characterized using X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Cyclic Voltammetry (CV) and chronoamperometry (CA) analysis. FESEM results show that on increasing growth temperature the morphology changes from clusters into mixture of rods and flakes. XPS analysis reveals the formation of MnO2. Then these particles were immobilized on Pt electrode. A platinum (Pt) electrode modified with low dimensional MnO2 was investigated as a chronoamperometric (CA) sensor for hydrogen peroxide sensing (H2O2). The sample prepared at 100 degrees C shows good electrocatalytic ability for H2O2 sensing when compared with the samples prepared at 40 degrees C and 80 degrees C. At an operating potential of 0.3 V vs. Ag/AgCl catalytic oxidation of the analyte is measured for chronoamperometric (CA) monitoring. The CA signals are linearly proportional to the concentration of H2O2. It is also found that the morphology of the nanostructure plays a vital role in the detection of H2O2. (C) 2014 Elsevier Ltd. All rights reserved.

Stimuli-responsive colorimetric and NIR fluorescence combination probe for selective reporting of cellular hydrogen peroxide

Hydrogen peroxide (H2O2) is a key reactive oxygen species and a messenger in cellular signal transduction apart from playing a vital role in many biological processes in living organisms. In this article, we present phenyl boronic acid-functionalized quinone-cyanine (QCy-BA) in combination with AT-rich DNA (exogenous or endogenous cellular DNA), i.e., QCy-BA subset of DNA as a stimuli-responsive NIR fluorescence probe for measuring in vitro levels of H2O2. In response to cellular H2O2 stimulus, QCy-BA converts into QCy-DT, a one-donor-two-acceptor (D2A) system that exhibits switch-on NIR fluorescence upon binding to the DNA minor groove. Fluorescence studies on the combination probe QCy-BA subset of DNA showed strong NIR fluorescence selectively in the presence of H2O2. Furthermore, glucose oxidase (GOx) assay confirmed the high efficiency of the combination probe QCy-BA subset of DNA for probing H2O2 generated in situ through GOx-mediated glucose oxidation. Quantitative analysis through fluorescence plate reader, flow cytometry and live imaging approaches showed that QCy-BA is a promising probe to detect the normal as well as elevated levels of H2O2 produced by EGF/Nox pathways and post-genotoxic stress in both primary and senescent cells. Overall, QCy-BA, in combination with exogenous or cellular DNA, is a versatile probe to quantify and image H2O2 in normal and disease-associated cells.

Identification and measurement of fatty acids, amino acids in roe of tuna fish (Thunnus tonggol) and its TVB and peroxide value during cold storage

The first aim of this research was to identify fatty acids, amino acids composition of Thunnus tonggol roe and their changes during cold storage (-18'C). The second aim was to determine the changes of moisture, protein, fat and ash contents of the roe during one year cold storage (-18'C). 60 samples of longtail tuna (Thunnus tonggol) ovaries were randomly collected form Bandar-e-Abbas landings. The samples were frozen at-30'C and kept in cold store at -18'C for one year. According to a time table, the samples were examined for identification of fatty acids, amino acids, moisture, protein, fat, ash, peroxide and T.V.N. and their changes were evaluated during this time. The results showed that 26 fatty acids were identified. The unsaturated fatty acids (UFA) and saturated fatty acids (SFA) were 62.33 and 37.6%, respectively, in fresh roe. So that, DHA (C22:6) and oleic acid (C18:1) had high amounts (24.79 and 21.88%) among the UFA and palmitic acid (C16:0) was the most content (22.75%) among the SFA. The PUFA/SFA was 0.91. Also, 17 amino acids were identified that essential amino acids (EAA) and nonessential amino acids (NE) were 10478 and 7562 mg/100g, respectively, and E/NE was 1.38. Among the EAA and NE, lysine (2110mg/100g) and aspartic acid (1924 mg/100g) were the most contents. Also, results showed that moisture, ash, protein and fat contents were 72.74, 1.8, 19.88 and 4.53%, respectively, in fresh roe. The effects of freezing and cold storage on the roes showed that UFA and SFA contents have reached to 49.83 and 48.07%, respectively, at the end of cold storage. It indicated that these compounds change to each other during frozen storage. Also, n-3 and n-6 series of fatty acids were 32.75 and 1.61% in fresh roe. But their contents decreased to 22.96 and 1.25% at the end of period. Among the fatty acids, 22:6 and C16:0 had the most changes. The changes of fatty acids were significantly at 95% level except for C15:1, C18:3(n-3) and C20:4(n-6). All of the amino acids decreased in frozen storage and their changes were significantly (P<0.05). EAA was 7818 mg/100g and E/NE was 1.27 at the end of storage period. Among the amino acids, leucine and lysine had the most changes. Moisture, ash, protein and fat contents were 70.13, 1.82, 19.4 and 6.51%, respectively, at the end of storage period. The peroxide value and T.V.N. increased during storage. So that, their contents have reached to 5.86 mg/kg and 26.37 mg/100 g, respectively, at the end of frozen storage. The best shelf life of Thunnus tonggol roe was 6 or 7 months, because of lipid oxidation and increasing of peroxide.

Evaluate the efficiency of hydrogen peroxide and levaemisole hydrochloride in the treatment of Persian sturgeon, Chinese carp eggs and juveniles

During a two years research hydrogen peroxide efficacy evaluated for Persian sturgeon, Chinese carps and common carp eggs. These series of the experiments conducted in various conditions different concentration of hydrogen peroxide include 250, 500, 750, 1,000 1,500 2,000 3,000 and 9,000 PPM used as ten and fifteen minutes baths, compared with Malachite green and natural control . In the next phase effect of Levaemisole hydrochloride as an immunostimulator which applied as 5 mg/I in twenty minutes baths from day sixth after hatch evaluated by daily mortality rate and leukocytes counts. The results shown that according fertilization percent and temperature condition hydrogen peroxide at 1,000 and 1,500 PPM concentrations is a effective antifungal agent during incubation periods of Persian sturgeon and even sometimes increasing hatching rates significantly comparing with natural controls and Malachite green. In Chinese carps although hydrogen peroxide controls water molds but it is not recommended in high temperatures because it make shortened incubation time and mold infections will decrease. Also the results shown 750 PPM concentration of hydrogen peroxide in common carp eggs controls water moulds infections and increase hatching rate significantly comparing with Malachite green and natural control. Daily mortality rates accessing of Persian sturgeon fries show that 20 minutes baths of 5mg/1 levamisole hydrochloride decreases daily mortality rate during yolk sac absorption. Nitrogenous compounds: nitrate and ammonium differ significantly between treated tanks with control. Blood leucocytes concentrations as an immune index was different significantly in treated fishes by levamisole hydrochloride comparing with controls. In Chinese carps because yolks sac absorption time is short there is not necessary to use the levamisole hydrochloride. Although treated larvae were more active than controls. As a result our suggestions is to use hydrogen peroxide in Persian sturgeon and common carp artificial propagation and also suggest the use levamisole hydrochloride for Persian sturgeon beside management method in stress and pollution condition

Evaluation and comparison of ozone, hydrogen peroxide and physical treatment on fungal infection prevention and hatching rate of Iranian sturgeon (Acipenser persicus)

Ozone due to having low half-life and devoid of environmental harmful effects is recognized as one of the most effective disinfectant and fungicide in aquaculture. The objective of this study is to consider the effects of periodicay ozonation, hydrogen peroxide treatment, and physical treatment capability in hatching rate enhancement. Three concentrations of 0.05, 0.1 and 0.15 ppm ozone (10 min) and peroxide hydrogen with dose of 500 and 1000 ppm in two procedures accompanied with physical treatment and without physical treatment were examined on hatching rate. In the first year, Egg ozonation (0.1 ppm) with physical treatment have been resulted the greatest hatching rate (81.4%). In the second year, egg treatment with 1000 ppm hydrogen peroxide with physical treatment have been showed the greatest hatching rate (78%). Average hatching rate for the blank control treatment (without disinfectin and physical treatment) was 32.7%. From the economic viewpoint, 0.05 ppm ozone with physical treatment, due to considerable minimizing at consumption energy and ozonation system retention costs, indicated as the best treatment than other ozone treatments for fungal control. Very low correlation (r=-0.14) have been observed between hatchery water temperature and fungal infection percentage in control treatment.

Molecular Dynamics Simulation on Characteristics of Decomposition of Methane Hydrate in the Presence of Hydrogen Peroxide Solution

In this work, the characteristics of the decomposition of methane hydrate Structure I (SI) in the presence of hydrogen peroxide solution is investigated using the molecular dynamics simulation. The mechanism of the transformation process from the solid hydrate to the liquid is analyzed with the effect of hydrogen peroxide (HP) solution. In addition, the effect of ethylene glycol (EG) with the same molar concentration with HP on the methane hydrate dissociation is also studied. The results illustrate that both HP and EG promote well the hydrate dissociation. The work provides the important reference value for the experimental investigation into the promotion effect of HP on the hydrate dissociation.

Fluorescence Hydrogen Peroxide Probe Based on a Microstructured Polymer Optical Fiber Modified with a Titanium Dioxide Film

A highly sensitive microstructured polymer optical fiber (MPOF) probe for hydrogen peroxide was made by forming a rhodamine 6G-doped titanium dioxide film on the side walls of array holes in an MPOF. It was found that hydrogen peroxide only has a response to the MPOF probe in a certain concentration of potassium iodide in sulfuric acid solution. The calibration graph of fluorescence intensity versus hydrogen peroxide concentration is linear in the range of 1.6 x 10(-7) mol/L to 9.6 x 10(-5) mol/L. The method, with high sensitivity and a wide linear range, has been applied to the determination of trace amounts of hydrogen peroxide in a few real samples, such as rain water and contact lens disinfectant, with satisfactory results.