Threonine-FX dosimeter for food irradiation

A detailed study for the spectrophotometric readout method for L-threonine powder, [CH₃CH(OH)CH(NH₂)COOH], was done. In this method, 400 mg unirradiated/irradiated L-threonine powder was dissolved in 10 ml of a solution which contains 3×10⁻⁴ mol dm⁻³ ferrous ammonium sulphate and 1.7×10⁻⁴ mol dm⁻³ xylenol orange (XO) in aerated aqueous 0.17 mol dm⁻³ sulphuric acid (FX). The peroxy radicals produced from irradiated threonine oxidize ferrous ions and XO forms a complex with ferric ions as well as controls the chain length of ferrous ion oxidation. The plot of absorbance at 556 nm against dose is linear in the dose range 20–400 Gy and doses down to about 1 Gy can be measured using 10-cm path cells. Response of the dosimeter is independent of irradiation temperature above 20. A dose of 50 Gy–10 kGy can be measured dissolving 50 mg threonine powder in 10 ml of a solution which contains 3×10⁻⁴ mol dm⁻³ ferrous ammonium sulphate and 1.3×10⁻⁴ mol dm⁻³ XO in aerated aqueous 0.06 mol dm⁻³ sulphuric acid (FX). The plot of absorbance at 552 nm against dose is non-linear. However dosimeter shows linear dose response up to 1000 Gy. Irradiated threonine powder is stable for about 3 months. The reproducibility of the method is better than ±2%. This dosimeter is very useful as transfer dosimeter for food irradiation programme.     

Applicability of the Sunna dosimeter for food irradiation control

The quick development concerning the commercial application of food irradiation in the USA recently resulted in growing marketing of irradiated red meat as well as irradiated fresh and dried fruits. These gamma and electron irradiation technologies require specific dosimetry systems for process control. The new version of the Sunna dosimeter has been characterized in gamma, electron and bremsstrahlung radiation fields by measuring the optically stimulated luminescence (osl) at 530 nm both below and above 1 kGy, i.e. for disinfestation and for meat irradiation purposes. No humidity and no significant dose rate effect on the green osl signal was observed. The temperature coefficient was determined from 0°C up to about 40°C and to stabilize the osl signal after irradiation a heat treatment method was introduced. Based on these investigations the Sunna ‘gamma’ film is a suitable candidate for dose control below and above 1 kGy for food irradiation technologies.     

Enhanced protonation of cresol red in acidic aqueous solutions caused by freezing

The protonation degree of cresol red (CR) in frozen aqueous solutions at 253 or 77 K, containing various acids (HF, HCl, HNO3, H2SO4, and p-toluenesulfonic acid), sodium hydroxide, NaCl, or NH4Cl, was examined using UV/Vis absorption spectroscopy. CR, a weak organic diacid, has been selected as a model system to study the acid-base interactions at the grain boundaries of ice. The multivariate curve resolution alternating least-squares method was used to determine the number and abundances of chemical species responsible for the overlaying absorption visible spectra measured. The results showed that the extent of CR protonation, enhanced in the solid state by 2-4 orders of magnitude in contrast to the liquid solution, is principally connected to an increase in the local concentration of acids. It was found that this enhancement was not very sensitive to either the freezing rate or the type of acid used and that CR apparently established an acid-base equilibrium prior to solidification. In addition, the presence of inorganic salts, such as NaCl or NH4Cl, is reported to cause a more efficient deprotonation of CR in the former case and an enhanced protonation in the latter case, being well explained by the theory of Bronshteyn and Chernov. CR thus served as an acid-base indicator at the grain boundaries of ice samples. Structural changes in the CR molecule induced by lowering the temperature and a presence of the constraining ice environment were studied by the absorption and 1H NMR spectroscopies. Cryospheric and atmospheric implications concerning the influence of acids and bases on composition and reactivity of ice or snow contaminants were examined.     

Dosimetric characteristics of aqueous solution of crystal violet for applications in food irradiation

Aqueous solution of crystal violet has been evaluated spectrophotometrically as a gamma-ray chemical dosimeter. The response of the chemical dosimetric system has also been investigated under different environmental conditions, such as light and temperature. In the present study the response has been measured at two wavelengths; 588 nm (λ_max of the irradiated solution) and 500 nm. The response of the crystal violet dosimeter was linear in the dose range of 50–550 Gy at pH 5.6 when absorption measurements were made at 588 and 500 nm. The response of the crystal violet dosimeter during post-irradiation storage at room temperature in dark showed slight decrease in absorbance at 588 and 510 nm but the response was almost stable at 460 nm. For higher doses, the change in the response was greater as compared to the low doses. Post-irradiation stability during diffused sunlight showed significant decrease in the response for higher dose at 588 and 510 nm and slower decrease in the response for lower dose at the above mentioned wavelengths. However the response was almost stable up to 97 days at 460 nm for higher and lower doses. At 4 °C, the decrease in the absorbance was slower at 588 and 510 nm while the response was almost constant at 460 nm. At higher temperatures, such as 40 °C, the decrease in the absorbance was greater at 588 and 510 nm while at 460 nm the absorbance was almost constant for about 3 months.     

Characterization and formation mechanism of the precipitates generated by irradiation of dicyclohexano-18-crown-6 aqueous solution

Dicyclohexano-18-crown-6 (DCH18C6) aqueous solution was irradiated using ⁶⁰Co source and precipitates containing yellow transparent blocks (PA) and powders (PB) were obtained. TGA analysis confirms that both PA and PB have higher thermal stability than DCH18C6. Both DSC and GPC results suggest that PA might be oligomer and PB were ultrahigh molecular weight polymers. The FTIR spectra indicate that both PA and PB have similar chemical structures containing carboxyl and hydroxyl groups. By using scavengers, it was found that the formation of PA and PB is attributed to the radiation-induced radical polymerization of DCH18C6, and ·OH radical produced by water radiolysis might be a critical species for the formation of PA and PB. These studies help to understand the radiation chemistry behavior of DCH18C6 in the reprocessing of nuclear fuel.     

Characterization of photoproducts of m-THPP in aqueous solution

This study examined the nature of photoproducts after pulse laser irradiation (647.5 nm) of 5,10,15,20-tetrakis(meso-hydroxyphenyl)porphyrin (m-THPP) (10 micromol/L) in ethanol-water (1/99, vol/vol) solution. Spectroscopic measurements (UV-visible absorption and fluorescence) and mass spectrometry techniques (matrix-assisted laser desorption-ionization [MALDI] coupled with time-of-flight mass spectrometer [TOF-MS] or tandem time of flight mass spectrometer [TOF/TOF-MS]) were used to follow photomodifications. Spectroscopic measurements evidenced photomodification as the main process after m-THPP irradiation. Three oxidized photoproducts at m/z 693.25, 695.24 and 713.25 were characterized by MS. After prolonged irradiation new isotopic distributions were registered at m/z 1355.41, 2031.57, 2707.80 and 3383.98 with MALDI-TOF-MS and TOF/TOF-MS. These new photoproducts were attributed to covalent oligomeric structures as dimer, trimer, tetramer and pentamer of m-THPP.     

Photodimerization of 7,8-dihydroneopterin in aqueous solution under UV-A irradiation

7,8-Dihydroneopterin (H(2) Nep) is secreted during the oxidative burst of stimulated macrophages. The photochemistry of H(2) Nep was investigated in neutral aqueous solutions exposed to UV-A radiation (320-400nm) at room temperature. The kinetics were followed by UV/Vis spectrophotometry and HPLC, whereas the photoproducts were analyzed by electrospray ionization mass spectrometry. Excitation of H(2) Nep leads to the formation of isomeric dimers with molecular masses equal to exactly twice the molecular mass of the reactant. The corresponding quantum yield of H(2) Nep consumption (Φ(-R) =(3.8±0.5)×10(-2)) was independent of O(2) and reactant concentrations. Mechanistic implications are discussed.     

Photodegradation of Congo red in aqueous solution on ZnO as an alternative catalyst to TiO2

In this research, the efficiency of ZnO and TiO₂ was compared by photocatalytic degradation of Congo red azo dye. The effects of some parameters such as pH, dye concentration and irradiation time on the degradation rate of dye solution were also examined. In addition, the aggregation feature of Congo red was studied by using UV-Vis spectroscopy techniques. The recovery of the ZnO catalyst was also investigated.     

Adsorption of Congo red from aqueous solution onto calcium-rich fly ash

The adsorption of Congo red from solution was carried out using calcium-rich fly ash with different contact times, concentrations, temperatures, and pHs. While the amount of dye adsorbed per unit weight of fly ash increases with increasing concentration and temperature, it decreases slightly with increasing pH. The adsorption was between 93 and 98% under the conditions studied. Kinetic studies showed that the adsorption process obeyed the pseudo-second-order kinetic model. It was also determined that the adsorption isotherm followed Freundlich and Dubinin-Radushkevich models. From thermodynamic studies, it was seen that the adsorption was spontaneous and endothermic. Desorption studies suggested that desorption was 29.18% in the presence of 0.1 N HCl and was 47.21% in the presence of CH(3)COOH (50% v/v). This indicated that most of the dye was held by fly ash via chemisorption as well as ion exchange. Furthermore, FTIR study also shows that a chemisorption process occurs between CR and fly ash, probably indicating dye/fly ash complexing.     

Post-irradiation stability of response of an aqueous coumarin dosimeter

Aqueous solution of coumarin (-benzopyrone) has been evaluated spectrophotometrically as a -ray dosimeter. In the present study measurements have been made at peak wavelength of 347 nm as well as at two other wavelengths (i. e. 360 and 370 nm). The response of the dosimeter with respect to absorbed dose is linear in the range of 0.05 to 0.5 kGy when absorption measurements are made at 347 nm. However, this dose range can be increased up to 0.8 kGy if analyzed at longer wavelengths of 360 and 370 nm. Postirradiation stability at room temperature in the dark show that the response increases gradually till 6 d. Afterwards the response is almost stabilized up to 42 d at all the wavelengths studied.     

Study of uranium biosorption process in aqueous solution by red beet peel

Journal of Radioanalytical and Nuclear Chemistry - Red beet peel was utilized for U(VI) removal in a batch system. The characterization of prepared biosorbent was performed by Fourier transform...     

Characterization of the aggregates of N-alkyl-N-methylpyrrolidinium bromide surfactants in aqueous solution

We have characterized a new class of surfactant molecules using fluorescence spectroscopic and light-scattering techniques. Our results suggest that this homologous series of N-alkyl-N-methlypyrrolidinium bromide (CnMPB) surfactants with n = 10, 12, 14, 16, and 18 represents a bridge between the well-characterized alkyltrimethylammonium bromide (CnTAB) and dialkyldimethylammonium bromide (di-CnDAB) surfactant series. For the smaller members of the CnMPB series with n = 10, 12, and 14, our results are consistent with the formation of spherical micelles as the surfactant concentration is increased. With increasing alkyl chain length, we observe that the critical micelle concentration decreases and the aggregation number increases, typical of single-tail surfactants. For C16MPB, the formation of micelles at dilute concentrations (0.10 mM) is likely, followed by the coexistence of micelles and small unilamellar vesicles at higher concentrations up to 0.82 mM where only vesicles are present. For C18MPB, our data are consistent with the formation of vesicles only. We demonstrate in this study that the combination of spectroscopic and light-scattering methods is a powerful approach to reveal aspects of aggregate structure and morphology in aqueous CnMPB surfactant systems. In particular, the sensitivity of the fluorescence probe prodan to the polarity of its microenvironment enables the rich complexity of surfactant aggregates exhibited by this series of amphiphilic molecules to be detected.     

Use of the dichromate solution as a dosimeter for high dose and high dose rate

The radiolytic reduction of Cr(VI) in N₂O-saturated aqueous solutions has been investigated over a large range of pH by steady state radiolysis. At pH 3 in the presence of formate as scavenger for ·OH, G(−Cr(VI)) is higher than the expected yield and a strong dose rate effect is observed. The solution cannot be used for dosimetry at this pH. The proposed mechanism to explain the enhanced response and the dose rate dependence involves the reduction of the unstable radiolytically produced Cr(IV) by HCO₂⁻. At pH 9.2 the reaction between Cr(IV) and formate is absent and no dose rate effect was observed up to 70 kGy min⁻¹, which makes this system particularly attractive as a dosimeter in the 0.1–10 kGy dose range. Radiation chemical aspects relating to the use of this system as a high-dose and high-dose rate chemical dosimeter are discussed.     

Characterization of micelle formation of dodecyldimethyl-N-2-phenoxyethylammonium bromide in aqueous solution

Aggregation behavior of dodecyldimethyl-N-2-phenoxyethylammonium bromide commonly called domiphen bromide (DB) was studied in aqueous solution. The Krafft temperature of the surfactant was measured. The surfactant has been shown to form micellar structures in a wide concentration range. The critical micelle concentration was determined by surface tension, conductivity, and fluorescence methods. The conductivity data were also employed to determine the degree of surfactant counterion dissociation. The changes in Gibb's free energy, enthalpy, and entropy of the micellization process were determined at different temperature. The steady-state fluorescence quenching measurements with pyrene and N-phenyl-1-naphthylamine as fluorescence probes were performed to obtain micellar aggregation number. The results were compared with those of dodecyltrimethylammonium bromide (DTAB) surfactant. The micelle formation is energetically more favored in DB compared to that in DTAB. The 1H-NMR spectra were used to show that the 2-phenoxyethyl group, which folds back onto the micellar surface facilitates aggregate formation in DB.     

Nitric oxide production by visible light irradiation of aqueous solution of nitrosyl ruthenium complexes

[Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](PF(6))(5) (L is NH(3), py, or 4-acpy) was prepared with good yields in a straightforward way by mixing an equimolar ratio of cis-[Ru(NO(2))(bpy)(2)(NO)](PF(6))(2), sodium azide (NaN(3)), and trans-[RuL(NH(3))(4)(pz)] (PF(6))(2) in acetone. These binuclear compounds display nu(NO) at ca. 1945 cm(-)(1), indicating that the nitrosyl group exhibits a sufficiently high degree of nitrosonium ion (NO(+)). The electronic spectrum of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex in aqueous solution displays the bands in the ultraviolet and visible regions typical of intraligand and metal-to-ligand charge transfers, respectively. Cyclic voltammograms of the binuclear complexes in acetonitrile give evidence of three one-electron redox processes consisting of one oxidation due to the Ru(2+/3+) redox couple and two reductions concerning the nitrosyl ligand. Flash photolysis of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex is capable of releasing nitric oxide (NO) upon irradiation at 355 and 532 nm. NO production was detected and quantified by an amperometric technique with a selective electrode (NOmeter). The irradiation at 532 nm leads to NO release as a consequence of a photoinduced electron transfer. All species exhibit similar photochemical behavior, a feature that makes their study extremely important for their future application in the upgrade of photodynamic therapy in living organisms.     

Ionization-induced nucleation above liquid beam of aqueous solution of phenol after IR laser irradiation

A continuous liquid flow of an aqueous solution of phenol (Ph) in a vacuum (a liquid beam) was irradiated with a pulsed IR laser at 3 μm, which was resonant to the OH-stretching vibration of the solvent water molecules. Phenol molecules ejected from the liquid beam were selectively ionized at about 0.5 mm above it by a pulsed UV laser (270–280 nm). The photoions thus produced were extracted in a pulsed electric field with a given residence time after the photoionization for mass analysis. It was shown that photoions, Ph⁺, were solvated into Ph⁺(H₂O)_n in a dense cloud of water vapor ejected from the liquid beam by IR irradiation.     

Characterization of creaming precipitate of tea catechins and caffeine in aqueous solution

The content of a crude precipitate formed by creaming, which was made from a catechin mixture and caffeine, was investigated by an integral volume of H-2 proton signals of tea catechins in the (1)H-NMR spectrum. Gallated catechins formed a crude precipitate more predominantly than non-gallated catechins. The 2,3-cis-non-gallated catechin (-)-epicatechin (EC) formed a 1?:?1 complex with caffeine, and 2,3-cis-gallated catechin (-)-epicatechin gallate (ECg) formed a 2?:?4 complex with caffeine. The π-π complexation site of EC with caffeine was only the A ring, whereas that of ECg included all aromatic rings, A, B, and B'. It was thought that the hydrophobicity of the 2?:?4 complex of ECg and caffeine was stronger than that of the 1?:?1 complex of EC and caffeine, with the result that the 2?:?4 complex of ECg and caffeine precipitated by creaming more predominantly than the 1?:?1 complex of EC and caffeine in aqueous solution.     

Polyetherimide functionalized carbon dots with enhanced red emission in aqueous solution for bioimaging

Red emissive carbon dots (CDs) are highly desired for biological applications. However, serious luminescence quenching of red emissive CDs in aqueous solution greatly hinders their application in high performance biological imaging. Herein, we reported a facile strategy to realize enhanced red emission of CDs in aqueous solution by surface modification with polyetherimide (PEI) via microwave heating method. High photoluminescence quantum yield (PLQY) of 25% was realized from the PEI functionalized CDs (CDs@PEI) in aqueous solution. The proposed PEI functionalization strategy not only protects the red emission against water molecules quenching, but also reverses the surface charges from negativity to positivity to promote cellular uptake of CDs, leading to clear cell imaging in red fluorescence region. More important, CDs@PEI exhibits much better photostability than commercial red emissive dye (MitoTracker red) in cell fluorescent imaging. Potential application of CDs@PEI on fast staining of cells for clonogenic assay has also been demonstrated.     

Lysozyme as diffusion tracer for measuring aqueous solution viscosity

Measuring tracer diffusion provides a convenient approach for monitoring local changes in solution viscosity or for determining viscosity changes in response to multiple solution parameters including pH, temperature, salt concentrations or salt types. One common limitation of tracer diffusion in biologically relevant saline solutions is the loss of colloidal stability and aggregation of the tracer particles with increasing ionic strength. Using dynamic light scattering to measure tracer diffusion, we compared the performance of two different types of tracer particles, polystyrene nanobeads vs. the small protein lysozyme, for viscosity measurements of saline solutions. Polystyrene beads provide reliable values for water viscosity, but begin flocculating at ionic strengths exceeding about 100 mM. Using lysozyme, in contrast, we could map out viscosity changes of saline solutions for a variety of different salts, for salt concentrations up to 1 M, over a wide range of pH values, and over the temperature range most relevant for biological systems (5–40 °C). Due to its inherently high structural and colloidal stability, lysozyme provides a convenient and reliable tracer particle for all these measurements, and its use can be readily extended to other optical approaches towards localized measurements of tracer diffusion such as fluorescence correlation spectroscopy.