Radiolysis study of genistein in methanolic solution

The aim of the present work was to identify products obtained from genistein by ionizing radiation and to enhance the antioxidant properties of genistein through radiation-induced transformation. Genistein dissolved in methanol was irradiated γ-rays at a dose of 100 kGy. NMR and (HR) EI-MS spectroscopy were used to identify radiolysis products (GM1 and GM2). We proposed that CH₂OH may be implicated in the formation GM1 and GM2 during radiolysis of genistein in methanol. The genistein in methanol solution showed higher DPPH radical scavenging activity after γ-irradiation. Then, the antioxidant activities of radiolysis products were evaluated and compared to those of genistein.     

Effect of gamma radiation on the mechanical and barrier properties of HEMA grafted chitosan-based films

Chitosan films were prepared by dissolving 1% (w/v) chitosan powder in 2% (w/v) aqueous acetic acid solution. Chitosan films were prepared by solution casting. The values of puncture strength (PS), viscoelasticity coefficient and water vapor permeability (WVP) of the films were found to be 565 N/mm, 35%, and 3.30 g mm/m² day kPa, respectively. Chitosan solution was exposed to gamma irradiation (0.1–5 kGy) and it was revealed that PS values were reduced significantly (p≤0.05) after 1 kGy dose and it was not possible to form films after 5 kGy. Monomer, 2-hydroxyethyl methacrylate (HEMA) solution (0.1–1%, w/v) was incorporated into the chitosan solution and the formulation was exposed to gamma irradiation (0.3 kGy). A 0.1% (w/v) HEMA concentration at 0.3 kGy dose was found optimal-based on PS values for chitosan grafting. Then radiation dose (0.1–5 kGy) was optimized for HEMA grafting. The highest PS values (672 N/mm) were found at 0.7 kGy. The WVP of the grafted films improved significantly (p≤0.05) with the rise of radiation dose.     

Radiation-induced grafting of stimuli-responsive binary monomers: PDMAEMA/PEGMEMA onto PP films

Both poly[2-(dimethylamino) ethyl methacrylate] (PDMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) were radiation grafted onto polypropylene films (PP) using gamma radiation from a ⁶⁰Co source. PP was pre-irradiated by gamma ray for modification following by grafted PDMAEMA and PEGMEMA by a one step method. Grafting was studied as a function of the pre-irradiation dose between 20 and 180 kGy, dose rate of 10.4 kGy/h, and monomer concentration 50% of PDMAEMA/PEGMEMA (1/1) in different solvents (toluene, acetone, and methanol). FTIR-ATR, TGA, and DSC were carried out in the characterization of the graft copolymer obtained. Stimuli-responsive behavior and critical pH point were studied by swelling in water. pH and thermo-responsive films of PE-g-(DMAEMA/PEGMEMA) presented a lower critical solution temperature (LCST) of 50 °C and critical pH point around 8.7.     

Effect of gamma irradiated sodium alginate on red amaranth (Amaranthus cruentus L.) as growth promoter

In order to study the growth promotion behavior of sodium alginate (SA) on vegetable (red amaranth, Amaranthus cruentus L.), 3% aqueous solution of SA was irradiated by γ-radiation (Co-60) of various total doses (12.5–50.0 kGy) at a dose rate of 3.5 kGy/h. Viscosity of the irradiated SA was found to decrease with increase in the radiation dose. The average molecular weight was also decreased from 10⁴ to 10³ orders. Red amaranth was cultivated in 18 different individual plots and SA solution (150 ppm) was applied on red amaranth after 10 days of seedlings at every 6 days interval. The morphological characters of vegetables were studied randomly in different unit plots. The irradiated SA of 37.5 kGy at 150 ppm solution showed the best performance. Dry matter of red amaranth significantly increased at 37.5 kGy of irradiated alginate treatment which was about 50% higher than that of the untreated samples. The effect of SA on red amaranth was found significant increase; i.e. plant height (17.8%), root length (12.7%), number of leaf (5.4%) and maximum leaf area (2%) compared to that of the control vegetative plant production.     

Degradation of alachlor herbicide by gamma radiation from cobalt-60 in aqueous and alcohol solution

Alachlor has been widely used in agriculture all over the world. It is suggested that it may be a carcinogen and an environmental estrogen. The aim of this work was to verify the degradation the alachlor by gamma radiation. Gamma radiation from ⁶⁰Co was used to degrade the alachlor herbicide in water and methanol solution. The alachlor in water and alcohol solution in the concentration of 100 mgL⁻¹ was irradiated with doses of 0.25–50 kGy, at dose rate 5–6 and 2.7 kGyh⁻¹. High performance liquid chromatography was used as an analytical technique to determine the degradation rate of herbicide studied.     

A novel amperometric sensor and chromatographic detector for determination of parathion

A novel amperometric sensor and chromatographic detector for determination of parathion has been fabricated from a multi-wall carbon nano-tube (MWCNT)/Nafion film-modified glassy-carbon electrode (GCE). The electrochemical response to parathion at the MWCNT/Nafion film electrode was investigated by cyclic voltammetry and linear sweep voltammetry. The redox current of parathion at the MWCNT/Nafion film electrode was significantly higher than that at the bare GCE, the MWCNT-modified GCE, and the Nafion-modified GCE. The results indicated that the MWCNT/Nafion film had an efficient electrocatalytic effect on the electrochemical response to parathion. The peak current was proportional to the concentration of parathion in the range 5.0×10^–9–2.0×10^–5 mol L^–1. The detection limit was 1.0×10^–9 mol L^–1 (after 120 s accumulation). In high-performance liquid chromatography with electrochemical detection (HPLC–ED) a stable and sensitive current response was obtained for parathion at the MWCNT/Nafion film electrode. The linear range for parathion was over four orders of magnitude and the detection limit was 6.0×10^–9 mol L^–1. Application of the method for determination of parathion in rice was satisfactory.     

Ionic silsesquioxane film immobilized on silica applied in the development of carbon paste electrode for determination of methyl parathion

A mesoporous silica-based hybrid material composed of silica xerogel modified with an ionic silsesquioxane, which contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group, was obtained. The silsesquioxane film is highly dispersed on the surface. This hybrid material was utilized to develop a carbon paste electrode (CPE) for determination of methyl parathion. Transmission FTIR, elemental analysis and N₂ adsorption–desorption isotherms were used for characterization of the material. The electrochemical behavior of methyl parathion was evaluated by cyclic voltammetry and differential pulse voltammetry. It was observed a linear response to methyl parathion in the concentration range from 1.25 × 10^?7 to 2.56 × 10^?6 mol L^?1 by employing the carbon paste electrode, in Britton–Robinson buffer solution (pH 6). The achieved detection limit (3 SD of the blank divided by the slope of calibration curve) was 0.013 µmol L^?1 and sensitivity was 6.3 µA µmol L^?1. This result shows the potentiality of this electrode for application as electrochemical sensor for methyl parathion.     

Molecularly imprinted nanoparticles-based electrochemical sensor for determination of ultratrace parathion in real samples

Molecularly imprinted polymer nanoparticles (nano-MIP), containing parathion selective sites, were synthesized by using suspension polymerization in silicon oil and then used for carbon paste electrode preparation. The obtained electrode was applied as an electrochemical sensor for parathion determination in different fruit and vegetable samples. Different factors including electrode composition, conditions of parathion extraction in the electrode and electrochemical measurement conditions were evaluated and then optimized by using various techniques of screening and response surface experimental designs. Electrode response to parathion (Res₁) and its selectivity for parathion (Res₂) were the desired responses. These responses were optimized simultaneously. After optimization, a sensor with high selectivity and picomolar detection limit were obtained. It was shown that the sensor response to parathion concentration was linear in the concentration range of 0.05 to 150?nmol?L^?1. The detection limit of designed sensor was calculated equal to 0.02?nmol?L^?1. The developed determination method was properly used for ultra-trace level assay of parathion in different fruit and cabbage samples.     

Multivariate optimization of molecularly imprinted polymer solid-phase extraction applied to parathion determination in different water samples

In this work a parathion selective molecularly imprinted polymer was synthesized and applied as a high selective adsorber material for parathion extraction and determination in aqueous samples. The method was based on the sorption of parathion in the MIP according to simple batch procedure, followed by desorption by using methanol and measurement with square wave voltammetry. Plackett-Burman and Box-Behnken designs were used for optimizing the solid-phase extraction, in order to enhance the recovery percent and improve the pre-concentration factor. By using the screening design, the effect of six various factors on the extraction recovery was investigated. These factors were: pH, stirring rate (rpm), sample volume (V₁), eluent volume (V₂), organic solvent content of the sample (org%) and extraction time (t). The response surface design was carried out considering three main factors of (V₂), (V₁) and (org%) which were found to be main effects. The mathematical model for the recovery percent was obtained as a function of the mentioned main effects. Finally the main effects were adjusted according to the defined desirability function. It was found that the recovery percents more than 95% could be easily obtained by using the optimized method. By using the experimental conditions, obtained in the optimization step, the method allowed parathion selective determination in the linear dynamic range of 0.20-467.4 μg L⁻¹, with detection limit of 49.0 ng L⁻¹ and R.S.D. of 5.7% (n = 5). Parathion content of water samples were successfully analyzed when evaluating potentialities of the developed procedure.     

Voltammetric Sensor for the Determination of Parathion Using an Electropolymerized Poly(Carmine) Film Electrode

A voltammetric sensor for the determination of parathion has been developed based on the use of a poly(carmine) film electrode. The reduction of parathion at the poly(carmine) modified glassy carbon electrode (GCE) is studied by cyclic voltammetry (CV) and linear scan voltammetry (LSV). Parathion yields a well-defined reduction peak at a potential of −0.595 V on the poly(carmine) modified GCE in pH 6.0 phosphate buffer solution (PBS). Compared with that on a bare GCE, the reduction peak current of parathion is significantly enhanced. All the experimental parameters are optimized for the determination of parathion. The reduction peak current is linear with the parathion concentration in the range of 5.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹, and the detection limit is 1.0 × 10⁻⁸ mol L⁻¹.     

Effects of low-level gamma irradiation on the characteristics of fermented pork sausage during storage

The effect of gamma irradiation (0.5, 1, 2, and 4 kGy) on the quality of vacuum-packaged dry fermented sausages during refrigerated storage was evaluated. At Day 0 of irradiation, the pH, redness (CIE a^?), yellowness (CIE b^?), 2-thiobarbituric acid-reactive substances (TBARS) and volatile basic nitrogen (VBN) values of samples irradiated at 2 and 4 kGy were higher (p<0.05), but the CIE L^? values (lightness) were lower than those of the non-irradiated control (p<0.05). At<1 kGy irradiation, however, the pH, CIE L^?, CIE a^? and CIE b^?-value of samples were not significantly influenced by irradiation. The CIE a^?, and CIE b^?-values of samples irradiated at 2 and 4 kGy decreased with the increase of storage time. The VBN, TBARS, and CIE L^?-values of samples irradiated at 4 kGy were not changed significantly during refrigerated storage for 90 days (p>0.05). The total plate counts (TPC) and lactic acid bacteria (LAB) in the samples irradiated at 4 kGy were significantly lower (p<0.01) than those with lower irradiation doses. At the end of storage, the TPC, coliform, and LAB in the samples were not increased after irradiation at 1, 0.5 and 1 kGy, respectively. TPC and LAB were not detected in samples irradiated at 4 kGy at Day 90. In addition, no coliform bacteria were found in samples irradiated at 1 kGy during refrigerated storage. Sensory evaluation indicated that the rancid flavor of samples irradiated at 4 kGy was significantly higher, but aroma and taste scores were lower than those of the control at Day 3 of storage. Irradiation of dry fermented sausages at 2 kGy was the best conditions to prolong the shelf-life and decrease the rancid flavor without significant quality deterioration.     

Cholinesterase-based dipstick assay for the detection of organophosphate and carbamate pesticides

A cholinesterase (ChE)-based dipstick-type assay for the class-specific detection of organophosphate (OP) and carbamate (CM) pesticides was developed. The principle of the assay is based on inhibition of the activity of a ChE by these two families of pesticides, which is dependent on the concentration of pesticides. The proposed assay system is composed of a test strip with an acetylcholinesterase (AChE)-coated membrane and an enzyme substrate solution. The assay protocol involves incubation of the enzyme-coated strip in the pesticide-containing sample solution followed by incubation of the sample-treated strip in a chromogenic enzyme substrate solution. The color intensity is estimated by the naked eye or a reflectometer. Of the membranes tested as the enzyme support, Hybond N⁺ was the most suitable. Among the compounds tested as the enzyme substrate, indophenyl acetate was the best. The detectable concentration range of the dipstick assay for the OP and CM pesticides was 10⁻⁶-10² and 10⁻⁶-10⁰ μg mL⁻¹, respectively. The sensitivity of the dipstick assay to the oxidized form of parathion (paraoxon) was higher than to parathion. The strip showed a large matrix effect with pesticide-spiked lettuce samples, whereas it showed a small matrix effect with pesticide-spiked rice samples.     

Spectroscopic analysis of pindolol irradiated in the solid state

Pindolol ((2RS)-(1-(1H-indol-4-iloxy)-3- [(1-metyloetylo)amino]-2-propanol) in substantia was exposed to ionising radiation emitted by high energy electrons from an accelerator, in the standard sterilisation dose of 25 kGy and in higher doses from the range 50–400 kGy. The effects of irradiation were checked by spectrometric methods (UV, MS, FT-IR, EPR) and hyphenated methods (HPLC-MS) and the results were referred to those obtained for non-irradiated sample. EPR results indicated the presence of free radicals in irradiated samples, in the amount of 1.36 × 10¹⁶ spin g^?1 for 25 kGy and 3.70×10¹⁶ spin g^?1 for 400 kGy. The loss of pindolol content determined by HPLC was 1.34% after irradiation with 400 kGy, while the radiolytic yield of the total radiolysis for this dose of irradiation was 2.69×10⁷ mol J^?1. By means of HPLC-MS it was possible to separate and identify one product of radiolytic decomposition, which probably is 2-((R)-3-(1H-indol-4-yloxy)-2-hydroxypropylamino)propan-1-ol formed upon oxidation. In the range of sterilisation doses (25–50 kGy), pindolol was found to show high radiochemical stability and would probably be safely sterilised by the standard dose of 25 kGy.      

Electrochemical deposition of silicate–cetyltrimethylammonium bromide nanocomposite film on glassy carbon electrode for sensing of methyl parathion

A novel electrochemical sensor for methyl parathion based on silicate– cetyltrimethylammonium bromide nanocomposite film has been fabricated by electro-assisted deposition onto glassy carbon electrode in one-step via an electrochemical modulation of pH at the electrode/solution interface to promote controlled gelification of tetraethylorthosilicate sol, and was characterized with scanning electron microscopy, X-ray diffraction, and electrochemical impedance spectroscopy. The electrochemical sensing of methyl parathion on the film-modified electrode was investigated applying cyclic voltammetry and square wave voltammetry. Compared to the unmodified electrode, the shapes of the redox peaks were improved and the peak currents significantly increased. Experimental parameters such as deposition time, pH value, and accumulation conditions have been optimized. A linear relationship between the peak current and methyl parathion concentration was obtained in the range from 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.04 × 10 ⁻⁸ mol L⁻¹ (S/N = 3) after accumulation at 0 V for 120 s. The film electrode shows great promise for determination of methyl parathion in real samples.      

Determination of Parathion‐methyl in Vegetables by Fluorescent‐Labeled Molecular Imprinted Polymer

A novel sensor for the determination of parathion‐methyl based on couple grafting of functional molecular imprinted polymers (MIPs) was fabricated which is developed by anchoring the MIP layer on surfaces of silica particles embedded CdSe quantum dots by surface imprinting technology. The synthesized molecular imprinted silica nanospheres (CdSe@SiO₂@MIP) allow a high selectivity and sensitivity of parathion‐methyl via fluorescence intensity decreasing when the MIP material rebinding the parathion‐methyl molecule. Compared with the MIP fabricated in traditional method, the template of parathion‐methyl was easier to remove from the CdSe@SiO₂@MIP imprinted material. Under optimal conditions, the fluorescence intensity of parathion‐methyl at the imprinted sensor was detected by spectrofluorophotometer. The relative fluorescence intensity of CdSe@SiO₂@MIP decreased linearly with the increasing concentration of parathion‐methyl ranging from 0.013 mg·kg⁻¹ to 2.63 mg·kg⁻¹ with a detection limit (3δ) of 0.004 mg·kg⁻¹ (S/N=3), which is lower than the MIP in tradition. The imprinted film sensor was applied to detect parathion‐methyl in vegetable samples without the interference of other organophosphate pesticides and showed a prosperous application in the field of food safety.     

Radiolytic degradation of malathion and lindane in aqueous solutions

Degradation of malathion and lindane pesticides present in an aqueous solution was investigated on a laboratory scale upon gamma-irradiation from a ⁶⁰Co source. The effects of pesticide group, presence of various additives and absorbed dose on efficiency of pesticide degradation were investigated. Gamma-irradiation was carried out in distilled water solutions (malathion and lindane) and in combination with humic solution (HS), nitrous oxide (N₂O) and HS/N₂O (lindane) over the range 0.1–2 kGy (malathion) and 5–30 kGy (lindane). Malathion was easily degraded at low absorbed doses compared to lindane in distilled water solutions. Absorbed doses required to remove 50% and 90% of initial malathion and lindane concentrations in distilled water solutions were 0.53 and 1.77 kGy (malathion) and 17.97 and 28.79 kGy (lindane), respectively. The presence of HS, N₂O and HS/N₂O additives in aqueous solutions, significantly improved the effectiveness of radiolytic degradation of lindane. Chemical analysis of the pesticides and the by-products resulted from the radiolytic degradation were made using a gas chromatography associated with mass spectrometry (GC–MS). Additionally, the final degradation products of irradiation as detected by ion chromatography (IC) were acetic acid and traces of some anions (phosphate and chloride).     

The relations between absorbed dose,molecular mass distribution,and viscosity studied on aqueous solution of ovalbumin agglomerated by γ irradiation

The γ‐irradiation induced stepwise genesis of dimer, trimer, tetramer, and higher agglomerates in 1% ovalbumin aqueous solution was quantitatively followed by a SDS‐PAGE analytical method. The molecular mass distributions obtained in the dose interval form 0 to 2 kGy were used to calculate the gel dose by using Good's theory of cascade processes. The difference between the calculated value (3.5 kGy) and the measured value (8.5 kGy) is attributed to the competition between the agglomeration and the interradical conversion processes, which prevails in the higher dose region. It was estimated from the gel dose that 1 · 10²⁰ of intermolecular bonds per dm³ were necessary to form a gel from 1% ovalbumin solution. A dynamic viscosity of the solution was also measured simultaneously. A simple semiempirical equation was developed containing only one parameter—gel dose, D_g—and it fits the viscosity–dose data fairly well. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1729–1733, 2000     

Effect of gamma radiation on the physico-chemical properties of alginate-based films and beads

Alginate solution (3%, w/v) was prepared using deionized water from its powder. Then the solution was exposed to gamma radiation (0.1?25 kGy). The alginate films were prepared by solution casting. It was found that gamma radiation has strong effect on alginate solution. At low doses, mechanical strength of the alginate films improved but after 5 kGy dose, the strength started to decrease. The mechanism of alginate radiolysis in aqueous solution is discussed. Film formation was not possible from alginate solution at doses >5 kGy. The mechanical properties such as puncture strength (PS), puncture deformation (PD), viscoelasticity (Y) coefficient of the un-irradiated films were investigated. The values of PS, PD and Y coefficient of the films were 333 N/mm, 3.20 mm and 27%, respectively. Alginate beads were prepared from 3% alginate solution (w/v) by ionotropic gelation method in 5% CaCl₂ solution. The rate of gel swelling improved in irradiated alginate-based beads at low doses (up to 0.5 kGy).     

Determination of individual rare earth elements in Vietnamese monazite by radiochemical neutron activation analysis

Radiochemical neutron activation analysis (RNAA) has been applied for determination of rare earth elements (REE) in Vietnamese monazite. The chemical separation procedure used is based on the chromatographic elution of rare earth groups, after the separation of²³³Pa(Th) in irradiated monazite samples by coprecipitation with MnO₂, the rare earth elements were retained by Biorad AG1×8 resin column in 10% 15.4M HNO₃-90% methanol solution. The elution of heavy rare earth (HREE) and middle rare earth (MREE) groups was carried out with 10% 1M HNO₃-90% methanol and 10% 0.05M HNO₃-90% methanol solution, respectively; while the light rare earths (LREE) were eluted from the column by 0.1M HNO₃ solution. The accuracy of the method was checked by the analysis of granodiorite GSP-I and the rare earth values were in good agreement.     

Effect of gamma irradiation on microbiological,chemical and sensory characteristics of licorice root product

Licorice root products were irradiated at doses of 0, 5, 10, 15 and 20 kGy in a ⁶⁰Co package irradiator. Irradiated and unirradiated samples were stored at room temperatures. Microbial population on product, chemical changes and sensory properties of produced solution of licorice root products were evaluated after 0 and 12 months of storage. The results indicated that gamma irradiation reduced the counts of microorganisms on licorice root products. D₁₀ of total count and klebsiella spp. were about 1.4 and 0.7 kGy, respectively. The mineral ions (Na, Ca and K) concentration in solution produced from irradiated products were lower than non-irradiated ones. Glycyrrhezinic acid and maltose concentration in solution produced from irradiated products were higher than non-irradiated ones. Sensory evaluation indicated that no significant differences (P<0.05) were found between solution produced from irradiated and unirradiated products in color, flavor, texture, or taste.