Post-irradiation stability of polyvinyl chloride at sterilizing doses

Post-irradiation stability of plasticized PVC irradiated by ⁶⁰Co gamma ray at sterilizing doses has been studied. Effects of irradiation upon chemical structure, mechanical properties and rheological behaviour of samples contained different amounts of Di(2-ethylhexyl)phthalate as plasticizer have been investigated. Formation of conjugated double bonds, carbonyl and hydroxyl groups have been followed by UV and FTIR spectrometers up to 6 months after irradiation. FTIR spectra of irradiated samples showed no significant changes in carbonyl and hydroxyl groups even 6 months after irradiation. However, changes in UV-visible spectra was observed for the irradiated samples up to 6 months post-irradiation. This has been attributed to the formation of polyenes which leads to the discoloration of this polymer. Despite a certain degree of discoloration, it appears that the mechanical properties of PVC are not affected by irradiation at sterilizing doses. No change in the melt viscosity of the irradiated PVC samples with post-irradiation was observed, which is in consistent with the IR results.     

Characterization of aqueous solution of cresol red as food irradiation dosimeter

Dilute aqueous solution of cresol red has been evaluated spectrophotometrically as possible gamma rays dosimeter. A 0.10 mM solution of cresol red was irradiated by gamma rays using a cobalt-60 radiation source. The absorbance spectra of the unirradiated and irradiated solutions were recorded using double beam scanning spectrophotometer. The absorbance of the solution before and after irradiation was measured at 434 nm (λ_max) as well as at other wavelengths (415, 448 and 470 nm). Various parameters, such as Absorbance (A), ΔA, %A, -log A and log A_o/A_i were plotted against radiation dose, in order to check the response of cresol red solution and its possible use as chemical dosimeter. The response plots of A, ΔA, and %A versus absorbed dose showed that the solution can be used as a radiation dosimeter in a dose range up to 0.82 kGy. Using response plots of -log A and log A_o/A_i, the useful dose range can be extended up to 1.65 kGy; which are useful dose ranges for food irradiation applications. Stability studies of cresol red solution at different light and temperature conditions for pre- and post-irradiated storage of the dosimetric solutions suggested that aqueous solution of cresol red is highly stable in dark, under fluorescence light and at room temperature up to 150 days     

The response of the chlorobenzene-ethanol-trimethylpentane dosimeter to medium energy X-rays

Energy dependence of the radiation chemical yield of hydrochloric acid, G(HCl), of chlorobenzene-ethanol-trimethylpentane (CET) dosimetry system was investigated to medium energy X-rays (210, 150 and 120 kV maximum energy). In the dose range 50–150 Gy the concentrations of chloride ions were determined spectrophotometrically. Reference dosimetry for all measurements was carried out by the Fricke dosimeter. There was no change of radiation chemical yield of chloride ions with photon energy throughout the X-ray energy range applied in this work, i.e. down to the mean energy of about 50 keV.     

Post-irradiation degradation of polypropylene

We present the mechanical changes (elongation at break, tensile strength, modulus of elasticity) and electrical changes (volume and surface resistivity, tg, , breakdown voltage) ofisotactic polypropylene (PP) due to -radiation. Ageing of PP was achieved in air by using a¹³⁷Cs -source with 400 Ci activity; the dose rate was of 8·10⁴ rad/h, and the integrated doses ranged from 2 to 160 Mrad. Severe deterioration of mechanical properties was observed. The changes of electrical properties were not as significant as those of mechanical characteristics. These variations are caused by the increase in density of crosslinking chain-scission and by oxidative processes. The rate of extent of degradations has been evaluated by the growth of the hyydroxy and carbonylbands in the IR spectrum By using FTIR mapping, we have also investigated the degradation of PP which had been irradiated in air 15 years ago. We determined the contour lines of FTIR absorption bands of carbonyl groups at different regions of the cross-section of an irradiated sample. Dust particles of irradiated brittle PP were also studied. The FTIR showed that the carbonyl band is broad, indicating a mixtures of many different functional groups (ester, acid, ketone, lactones). We determined also the gel content at different irradiation doses.     

Effect of post-irradiation thermal treatments on the stability of gamma-irradiated glass dosimeter

A commercial window glass has been investigated as a routine high dose dosimeter for gamma irradiation. The irradiated samples showed rapid fading at room temperature immediately after irradiation. This short-term rapid fading was followed by a slow fading at long-term. This strong initial fading is a problem for dosimetry purposes. However, when the dosimeter is measured at the same time interval after irradiation, it maintains proportionality to dose. Calibration curves have to be used for different time intervals after irradiation. In order to improve post-irradiation stability dosimeters were submitted to different post-irradiation thermal treatments from (−20) up to 150 °C. After that, optical absorbance measurements were carried out up to 2 months at room temperature. The heating at 150 °C for 20 min was found to be the most suitable procedure for the removal of unstable entities responsible for the initial rapid fading. Due to these heat treatments, variation of response was found almost negligible 24 h after irradiation for several months. Calibration curves demonstrated the applicability of this glass as routine dosimeter in the dose range of 0.5–90 kGy.     

Electrospinning of chitosan derivative nanofibers with structural stability in an aqueous environment

We report a simple method to produce stable chitosan derivative nanofibers via electrospinning. A chitosan solution with lactate salt was electrospun to produce nanofibers, followed by thermal treatment to enhance fiber stability. Chemical and morphological analyses demonstrated that the resulting nanofibers were crosslinked via amidation between chitosan and lactate salt. These fibers exhibited sustained morphological and structural stabilities to serve as a scaffold for biomedical applications.     

Stability of response of the ferrous-cupric sulfate dosimeter at different temperatures

Aqueous solution of ferrous-cupric sulfate has been evaluated spectrophotometrically as radiation dosimeter and post-irradiation stability at different storage temperatures has been studied. The response curve drawn at a peak wavelength of 304 nm shows a linear response of up to 7 kGy. However, with proper calibration, the system can be used up to 14 kGy. At room temperature (ca. 25 °C) in the dark, the irradiated solution showed stable response up to about 12 h, followed by a small decrease in response up to 20 d. Post-irradiation storage at lower temperature (10 °C) shows no significant change in absorbance over a storage period of 6 d. However, for storage at higher temperature (40 °C) the dosimeter showed a stable response only up to a few hours and at longer storage times the response of the dosimeter increased.     

A study on dose response of NIPAM-based dosimeter used in radiotherapy

The newly manufactured N-isopropylacrylamide (NIPAM) polymer gel is composed of four components, i.e., gelatin, monomer (NIPAM), crosslinker (N,N’-methylenebisacrylamide, Bis), and antioxidant (tetrakis hydroxymethyl phosphonium chloride, THPC). In this study, we investigated the effects of gel composition on the dose response of NIPAM polymer gel. A statistical experiment to analyze the contribution of each composition to the linearity and sensitivity of NIPAM gel was performed. Results indicate that the amount of gelatin, NIPAM (15.17%), Bis, and THPC have dominant effects on the sensitivity of the gel, with contributions of 59.73, 15.17, 10.64, and 14.45%, respectively. The amount of gelatin and Bis mainly affected the linearity of the gel, with contributions of 44.70 and 50.99%, respectively. The linearity of most compositions of the gel was greater than 0.99 when (%C)/(%T) was lower than 8.0. Optimal (%C)/(%T) for higher sensitivity should be in the range of 4−9. The temporal stability experiment showed that the dose response curve attained stability at about 5 h after irradiation and persisted up to 3 months.     

Energy response of a thermoluminescent lithium fluoride disc dosimeter to beta-rays

In order to eliminate some drawbacks of thin detector with suitable window for measuring radiations of low penetrating power, the thermoluminescent LiF disc dosimeter was fabricated from phosphor of LiF with activators of magnesium and copper and inorganic binder of silica and alumina. The energy response of the LiF disc dosimeters to beta-rays was investigated by comparing with theoretical calculations and measurements with a parallel-plate ionization chamber. From the results obtained, the LiF disc dosimeter significantly underestimated the doses for low beta-ray energy (below 0.3 MeV), while its reading agreed well with the calculated ones for high energy (above 0.8 MeV). Nevertheless, it is suggested that the fabricated LiF disc dosimeter is useful to evaluate the skin dose from the practical point of view, since beta-ray less than 0.6 MeV is completely absorbed before reaching the skin covered with clothing.     

Post-irradiation oxidation of different polyethylenes

The radiation-induced oxidative degradation of polyethylenes (PEs) with different degrees of crystallinity was characterized after electron-beam irradiation and during storage at room temperature.UHMWPE, HDPE, LDPE, LLDPE and an ethylene-octene copolymer (Engage) were e-beam irradiated to 30 or 60 kGy in vacuum or in air and stored at room temperature in air. EPR spectroscopy was used to investigate macro-radicals produced during irradiation and their post-irradiation changes. FTIR spectroscopy was used to monitor changes in the polymer structure, induced by irradiation, and to follow post-irradiation oxidation.We found that the crystallinity and the size of the crystalline lamellae, in particular, play a major role on the post-irradiation effects. The low-crystallinity polyethylenes showed no oxidation or oxidation only to a small extent, even when irradiated and stored in air. On the contrary, development of post-irradiation oxidation was observed in HDPE and UHMWPE. We attribute these results to a different reactivity of the macro-alkyl radicals formed upon irradiation in the amorphous or in the crystalline phase. While the radicals formed in the amorphous phase decay in short time, the migration time of the radicals trapped in the crystalline phase to the amorphous one is a key factor, governing the oxidation process.     

Characterization of an LED based photoreactor to degrade 4-chlorophenol in an aqueous medium using coumarin (C-343) sensitized TiO2

A detailed performance evaluation of a simple high intensity LED based photoreactor exploiting a narrow wavelength range of the LED to match the spectrum of a dye in a photocatalysis system is reported. A dye sensitized (coumarin-343, lambda max = 446 nm) TiO 2 photocatalyst was used for the degradation of 4-chlorophenol (4-CP) in an aqueous medium using the 436 nm LED based photoreactor. The LED reactor performed competitively with a conventional multilamp reactor and sunlight in the degradation of 4-CP. Light intensities entering the reaction vessel were measured by conventional ferrioxalate actinometry. The results can be fitted by approximate first order kinetic behavior in this system. Hydroxyl radicals were detected by spin trapping EPR, and effects of OH radical quenchers on kinetics suggest that the reaction is initiated by these radicals or their equivalents. LEDs operating at competitive intensities offer a number of advantages to the photochemist or the environmental engineer via long life, efficient current to light conversion, narrow bandwidth, forward directed output, and direct current power for remote operation. Matching light source spectrum to chromophore is a key.     

Sunna 535-nm photo-fluorescent film dosimeter response to different environmental conditions

Evaluations on the influence of environmental variabilities on the red fluorescence component of the Sunna Model γ photo-fluorescent dosimeter^TM have previously been reported. This present paper describes the environmental effects on the response of the green fluorescence component of the same dosimeter, which is manufactured using the injection molding technique. The results presented include temperature, relative humidity, and light influences both during and after irradiation. The green fluorescence signal shows a significant dependence on irradiation temperature below room temperature at 1%/°C. Above room temperature (approximately 24–60°C), the irradiation temperature effect varies from −0.1%/°C to 1.0%/°C, depending on the absorbed dose level. For facilities with irradiation temperatures between 30°C and 60°C and absorbed dose levels above 10 kGy, irradiation temperature effects are minimal. Light-effects results indicate that the dosimeter is influenced by ultraviolet and blue wavelengths during irradiation as well as during the post-irradiation stabilization period (approximately 22 h), requiring the use of light-tight packaging. Results also show that the dosimeter exhibits negligible effects from ambient moisture during and after irradiation when in the range of 33–95% relative humidity.     

Supramolecular synthesis of coumarin derivatives catalyzed by a coordination-assembled cage in aqueous solution

A self-assembled Pd_4L_2 cage is employed as a water-soluble molecular flask for the synthesis of functionalized coumarins from a series of salicylaldehyde derivatives and cyanoacetates/malononitrile. The catalytic reaction features mild aqueous conditions and broad substrate scope. Crystal structures of the host-guest complexes for two substrates and one analogous intermediate have been obtained, shedding light on the supramolecular reaction mechanism. Michaelis-Menten kinetic studies were performed in one typical case, revealing that the rate of product formation has been enhanced by over 23-fold in contrast to the background reaction without cage. Moreover, the same reaction catalyzed by a smaller Pd_6L_4 cage gives a mixture of products and much lower yields, suggesting that fine-tuning on the size and symmetry of the cages' cavity is crucial for their applications in supramolecular catalysis.     

Gamma-ray response of a clear,crosslinked PMMA dosimeter,Radix W

Radix W, a clear poly(methyl-methacrylate) (PMMA) dosimeter was developed with improved properties compared to the conventional clear PMMA dosimeter, Radix RN15. PMMA with a glass transition temperature (T_g) higher than 120 °C was selected making it possible to measure doses in a wide range of 1 to 150 kGy. Dose rates of 2.5–10 kGy/h were tested and did not affect significantly the dose response. The influence of irradiation temperature was reduced compared with Radix RN15.     

Colloidal stability of aqueous nanofibrillated cellulose dispersions

Cellulose nanofibrils constitute an attractive raw material for carbon-neutral, biodegradable, nanostructured materials. Aqueous suspensions of these nanofibrils are stabilized by electrostatic repulsion arising from deprotonated carboxyl groups at the fibril surface. In the present work, a new model is developed for predicting colloidal stability by considering deprotonation and electrostatic screening. This model predicts the fibril-fibril interaction potential at a given pH in a given ionic strength environment. Experiments support the model predictions that aggregation is induced by decreasing the pH, thus reducing the surface charge, or by increasing the salt concentration. It is shown that the primary mechanism for aggregation upon the addition of salt is the surface charge reduction through specific interactions of counterions with the deprotonated carboxyl groups, and the screening effect of the salt is of secondary importance.     

Dose response and post-irradiation characteristics of the Sunna 535-nm photo-fluorescent film dosimeter

Results of characterization studies on one of the first versions of the Sunna photo-fluorescent dosimeter™ have previously been reported, and the performance of the red fluorescence component described. This present paper describes dose response and post-irradiation characteristics of the green fluorescence component from the same dosimeter film (Sunna Model γ), which is manufactured using the injection molding technique. This production method may supply batch sizes on the order of 1 million dosimeter film elements while maintaining a signal precision (1σ) on the order of ±1% without the need to correct for variability of film thickness. The dosimeter is a 1 cm×3 cm polymeric film of 0.5-mm thickness that emits green fluorescence at intensities increasing almost linearly with dose. The data presented include dose response, post-irradiation growth, heat treatment, dosimeter aging, dose rate dependence, energy dependence, dose fractionation, variation of response within a batch, and the stability of the fluorimeter response. The results indicate that, as a routine dosimeter, the green signal provides a broad range of response at food irradiation (0.3–5 kGy), medical sterilization (5–40 kGy), and polymer cross-linking (40–250 kGy) dose levels.     

Dose rate dependence of cellulose triacetate dosimeter and radiochromic film dosimeter

The doses of γ-rays and electron beams were evaluated by Fricke dosimetry and the responses of cellulose triacetate dosimeter (CTA) and radiochromic film dosimeter (RCF) to the two types of radiations were compared to investigate their dose rate dependence. Both the change in absorbance at 280 nm of CTA and that in absorbance at 510 nm of RCF caused by γ-irradiation were larger than those by electron-irradiation, when the dosimeters were irradiated to the same dose. The results in this study suggest that the responses of CTA and RCF are dependent upon dose rate.     

Quantitative structure-activity relationship of coumarin derivatives. Involvement of partition between aqueous and membrane phase

In order to understand the substrate behaviour of several 7-alkoxycoumarins and 7-alkoxy-4-alkylcoumarins towards the liver microsomal monooxygenase system, their lipophilic properties have been examined. As a model for the lipophilicity the reversed-phase liquid chromatographic retention parameter log kw has been used. In a system with methanol-water as the mobile phase and RP-18 (octadecylsilica) as the stationary phase, we found a quadratic relationship between the volume fraction of the organic solvent and the logarithm of the capacity factor (log k'). The extrapolation to a pure aqueous phase reveals a linear relationship of the theoretical capacity factor log kw with the chain length. This holds for 1-12 carbon atoms in the alkoxy chain and for zero to three carbon atoms in the alkyl chain. Moreover, the incremental effect of the methylene residues on the lipophilicity of the compounds (delta log kw/delta CH2) is found to be 0.60 +/- 0.01. If the coumarin derivatives are used as substates for the liver microsomal monooxygenase system, no systematic dependence of the enzymic data (Michaelis-Menten constant Km) on the lipophilic data (log kw) can be demonstrated. The metabolism of these compounds by the microsomal monooxygenase system seems not to be limited by the partition between the membrane and the aqueous phase. Whether other factors, e.g. the lateral diffusion of the substrates versus the membrane-bound enzyme system or enzyme active-site characteristics, govern the metabolism remains to be investigated.     

A coumarin based ICT probe for fluoride in aqueous medium with its real application

A new coumarin based hydrazone (receptor 1) synthesized by modifying one of our earlier reported receptor detected fluoride ion selectively through naked eye in aq. DMSO (5:95, v/v). It was also able to detect fluoride through naked eye in a toothpaste sample. The addition of 1 equiv. of fluoride as its tetrabutylammonium salt to the 5 × 10⁻⁵ M aq. DMSO solution of the receptor 1 produced red color while the similar addition of acetate produced faint pink color. The dihydrogenphosphate and a variety of other anions were not able to produce any significant color change with receptor 1 under similar experimental conditions. The corresponding UV-vis measurements showed a bathochromic shifting of 455 nm band of receptor 1 to 514 and 484 nm for fluoride and acetate, respectively. The non-linear fittings of corresponding UV-vis titration data in 1:1 binding equation yielded association constants in 10⁵:1 ratio for fluoride and acetate, respectively. The ¹H NMR titrations studies shade further light on their mode of binding with receptor 1. The quantum mechanical calculations through time dependant density functional theory (TD-DFT) using basis set b3lyp/6-311g** supported our experimental findings nicely.     

Effects of humidity and temperature during irradiation on the response of blue PMMA dosimeter

Effects of relative humidity conditions in the irradiation chamber and of temperature of the chamber on the response of 3 mm thick light blue poly (methyl methacrylate) sheets have been studied. The response was measured spectrophotometrically at 402, 450, 596 and 612 nm. The response of the dosimeter is independent of the relative humidity (12–97%) during irradiation if the response is measured within 24 h of irradiation. If the response is measured after longer storage time, the absorbance at 402 and 450 nm increases significantly. At these two wavelengths the response of the dosimeter is also independent of the temperature of the irradiation chamber in the range of 0 to 40 °C. However, at higher temperatures (60, 80 °C), the response is not uniform.