Thermal study of four irradiated imidazoline derivatives in solid state

Four imidazoline derivatives: antazoline (AN), naphazoline (NN), tymazoline (TM), xylometazoline (XM), in the form of hydrochlorides in solid phase have been subjected to high energy e-beam irradiation from an accelerator (~10 MeV) at a dose varied from 25 to 200 kGy. The effects of the irradiation have been assessed by DSC, X-ray diffraction, FTIR, EPR and TLC. The standard sterilisation dose of 25 kGy has been found to produce changes in the properties of one derivative (XM), two other ones (AN and TM) have been found sensitive to doses >100 kGy, whereas NN has been resistant to irradiation in the whole range studied (25–200 kGy). EPR results indicated that the changes taking place in the therapeutic substances studied are related to radical formation. The irradiation induced changes in colour, a decrease or increase in the melting point, changes in the XRD pattern, small changes in the shape of FTIR peaks and the presence of radiolysis products. The XM compounds cannot be sterilised by irradiation because of the radiation induced changes in its physico-chemical properties.     

The influence of radiation sterilization on thiamphenicol

The effect of ionising radiation, applied in the form of an electron beam, in the doses of 25, 100 and 400 kGy on the physical and chemical properties of thiamphenicol in solid phase has been studied by organoleptic analysis (form, colour, smell, solubility, clarity) and spectroscopic methods (UV, IR, EPR), chromatography (TLC), SEM observations, X-ray diffraction, polarimetry and thermal method (DSC). The above-discussed results have proved that on irradiation with a dose of 25 kGy no significant changes appear in thiamphenicol, apart from the formation of free radicals of the lifetime of over 352 days. On irradiation with much higher doses (100 and 400 kGy) no changes were observed in the IR spectra but the UV line intensities slightly increased at lambda(max)=266 and 273 nm, the colour of the powder changed, the radiolysis products appeared as detected by TLC, changes were also observed in the XRD, SEM pictures, the melting point values (DSC) and optical rotation. On the basis of DSC results a linear relation was found between the irradiation dose and the decrease in the melting point and increase in the enthalpy of melting, characterised by high correlation coefficients of r=0.9839 and 0.9622, respectively. Moreover, a linear relation was established between the optical rotation angle and the irradiation dose, alpha(D) ( degrees )=f(dose), characterised by the correlation coefficient r=0.9874. The results obtained indicate that thiamphenicol can be safely subjected to radiation sterilization by the standard dose of 25 kGy.     

DSC study of radiostability of 1,4-dihydropyridine derivatives

The effect of sterilisation by irradiation has been studied for the seven most often used in medicine derivatives of 1,4-dihydropyridine (nifedipine, nisoldipine, nicardipine, nitrendipine, nimodipine, felodipine and amlodipine). The sterilisation was performed for the compounds in the solid phase with an electron beam of the energy 10 MeV, at room temperature, using the irradiation doses from 20 to 400 kGy. The effects of the irradiation were studied by the methods SEM, DSC, XRD and TLC. The sterilisation with doses 20-100 kGy was found to cause no changes in the physico-chemical properties of the compounds, while the irradiation with higher doses (200-400 kGy) was found to induce changes in the colour, DSC spectrum and TLC picture. As follows from the TLC results, the main product of radiolysis of the compounds studied was a pyridine nitrozoderivative, which indicates the same mechanism of decomposition as in the process of photodegradation. The results prove that the 1,4-dihydropyridine derivatives being highly sensitive to visible and UV radiation are generally resistant to ionising radiation and thus can be subjected to sterilisation by irradiation. This revised version was published online in July 2006 with corrections to the Cover Date.     

DSC and spectroscopic studies of disulfiram radiostability in the solid state

The effect of ionising radiation on the physico-chemical properties of disulfiram (Antabuse, Esperal, bisdiethylthiocarbamoil disulphide) has been studied by DSC, FTIR, EPR, MS, TLC and HPLC. Sterilisation was carried out in the solid state, at room temperature and normal air humidity using the electron beam of 9.96 Mev from accelerator. All the measurements were made simultaneously for the irradiated and nonirradiated substance. It has been found that the drug studied in solid phase when subjected to an electron beam corresponding to the irradiation in the doses 10–100 kGy shows the presence of free radicals (EPR), and a change in colour from white to pale green-grey that disappears after solution in water or methanol. After the irradiation with the dose of 100 kGy, its melting point and enthalpy slightly decreased. Also the content of the active substance decreases (HPLC −1.5%, UV −3.6%, iodometric titration method −2.7%) and trace amounts of the radiolysis products appear (HPLC). The substance irradiated with the doses 10–50 kGy does not show changes in the melting point, in the content and presence of the radiolysis products. The EPR results have shown that free radicals disappear after about a year and the discolouring disappears with them. The results of this study have shown that disulfiram can be subjected to sterilisation by irradiation with no deterioration of its physico-chemical properties, but a long time of storage needed to remove free radicals and discolouration questions the economic justification for this type of sterilisation.     

Gamma irradiation of protein-based textiles for historical collections decontamination

In order to investigate the effect of gamma rays on cultural heritage materials, samples of silk and wool fabrics were subjected to accelerated ageing testing and then irradiated with different gamma-ray doses: 10 and 25 kGy. In the data analysis, combining thermal analysis (TG and DTG), infrared spectroscopy (FTIR-ATR) and mechanical tests allowed us to explore the changes in physical and chemical features for silk and wool, in relationship to the radiation doses. This analytical protocol offers a way to examine the behaviour of the textiles made of wool and silk within museum collections and their response to gamma-rays irradiation treatment. An exposure to a dose of 10 kGy did not cause significant changes in the tested properties; however, higher doses initiated irreversible loss in the physical and chemical stability of protein-based fabrics. Increasing the irradiation dose above 10 kGy has drastic effects in the loss of elasticity and the mechanical resistance of the tested yarns.     

Analytical study on irradiated methylxanthine derivatives

The effect of ionising radiation on the physico-chemical properties of three derivatives of xanthine: caffeine, theophylline and theobromine, has been studied. The above-drugs in the solid phase have been irradiated with E-beam of the energy 9.96 MeV with the doses varied from 25 to 400 kGy. The effects of the irradiation have been examined by differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR) and high-performance liquid chromatography (HPLC). The results have shown that the methylxanthine derivatives studied are resistant to ionising irradiation in the doses usually used for sterilisation (<50 kGy), which means that they are relatively radiochemically stable and can be sterilised by irradiation.     

The effect of gamma irradiation on mechanical, and thermal properties of recycling polyethylene terephthalate and low density polyethylene (R-PET/LDPE) blend compatibilized by ethylene vinyl acetate (EVA)

A study has been made on the compatibility of recycled polyethylene terephthalate (R-PET) and low density polyethylene (LDPE) blend in the presence of ethylene vinyl acetate (EVA) as a compatibilizing agent prepared by extrusion hot stretching process. EVA content in the blend as a compatibilizing agent was an enhancement effect on radiation crosslinking of R-PET/EVA/LDPE blends and the highest radiation crosslinking was obtained when the EVA content was reached at 10 % EVA when irradiated by gamma irradiation. Blends containing different (EVA) ratios were irradiated to different doses of gamma irradiation 25, 50 and 100 kGy. The effect of the compatibilizer and radiation on mechanical, thermal properties of R-PET together with LDPE and morphology has been investigated. It was found that gamma irradiation together with the presence of compatibilizing agent (EVA) has positive effect on the mechanical and thermal properties of R-PET/LDPE blend. The structural properties of R-PET/LDPE modified by gamma irradiation and EVA as compatibilizing agent was examined by SEM. Also, it was found that the optimum concentration of EVA and gamma irradiation dose was found to be 10 % EVA and 100 kGy, respectively.     

Effect of γ-irradiation on cotton-cellulose

The effect of high-energy irradiation on cotton-cellulose was studied in inert atmosphere and in the presence of oxygen. A decrease in the degree of polymerization from 1200 to 330 was measured after irradiation with a dose of 15 kGy (dose rate 100 Gy/h) and further gradual decrease was measured when the dose was increased up to 100 kGy. At lower doses a slight increase in crease recovery angle was found as compared to the unirradiated sample. In the FTIR spectra of the same sample the appearance of the absorbance of carbonyl groups (band at 1730–1750 cm⁻¹) was found as a consequence of the oxidative degradation. Cracks on the surface of the fibers were observed by scanning electron microscope on samples irradiated with doses higher than 100 kGy.     

The influence of nano silica particles on gamma-irradiation ageing of elastomers based on chlorosulphonated polyethylene and acrylonitrile butadiene rubber

The goal of this work was to study gamma irradiation ageing of rubber blends based on acrylonitrile butadiene rubber (NBR) and chlorosulphonated polyethylene rubber (CSM) reinforced by silica nano particles. The NBR/CSM compounds (50: 50, w/w) filled with different content of filler (0–100 phr) were crosslinked by sulfur. The vulcanization characteristics were assessed using the rheometer with an oscillating disk. The vulcanizates were prepared in a hydraulic press. The obtained materials were exposed to the different irradiation doses (100, 200, 300 and 400 kGy). The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) and swelling numbers were assessed before and after gamma irradiation ageing.     

Comparative study of effect of low and medium dose rate of γ irradiation on microporous polysulfone membrane using spectroscopic and imaging techniques

The effect of low (LDR) and medium dose rate (MDR) of γ irradiation at low doses (0-100 kGy) on the structural and chemical changes of microporous polysulfone (PSf) membrane has been studied using UV-vis, FTIR, SEM and dead-end filtration techniques. PSf membrane was cast by phase inversion method. Irradiation was done at room temperature in air media. The doses chosen were 0-100 kGy for LDR and 0-50 kGy for MDR; they were below and above sterilization dose. Analysis of UV-vis and IR spectra and SEM images obtained suggested that chain scissions and crosslink had occurred simultaneously in the irradiated membranes in both cases. This radio-oxidation effects observed start at a very low dose i.e. 1.66 kGy and increase with increase in dose. It is supported by the flux values obtained; it is increased with increase in dose. The results indicate that a very low dose γ irradiation was able to change the physicochemical characteristics of microporous PSf membrane which depend on dose rate of exposure.     

Effects of gamma irradiation on chemical composition and ruminal protein degradation of canola meal

Gamma irradiation of canola meal (at doses of 25, 50 and 75 kGy) could alter its ruminal protein degradation characteristics by cross-linking of the polypeptide chains. This processing resulted in decrease (linear effect, P<0.001) of ruminal protein degradation and increase (linear effect, P<0.001) of intestinal protein digestibility. The results showed that gamma irradiation at doses higher than 25 kGy can be used as a cross-linking agent to improve protein properties of supplements in ruminant nutrition.     

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.      

Changes in physicochemical and mechanical properties of γ-irradiated polypropylene syringes as a function of irradiation dose

The effect of γ-irradiation on mechanical, thermal, physicochemical and structural properties of polypropylene (PP) syringes was studied. Irradiation doses of 30, 60 and 120 kGy were used with non-irradiated PP syringes serving as control samples. Irradiation caused a significant deterioration in mechanical properties of samples. The compression strength of whole syringe body decreased with increasing irradiation dose. Similarly % extension at break decreased with increasing irradiation dose. Of the physicochemical properties tested, both degree of yellowness and extractable radiolysis products increased with increasing irradiation dose. Melting temperature as well as specific melting enthalpy decreased with increasing irradiation dose. Minor differences in FTIR spectra were observed, mainly in the region of 1720 cm⁻¹, corresponding to the absorption of carbonyl compounds indicating the formation of increased amounts of oxidation products at high irradiation doses. Gas chromatography- mass spectroscopy analysis indicated the formation of a number of radiolysis compounds as a result of irradiation. The number and concentration of these compounds increase progressively with increasing dose until 60 kGy. At the same time a number of compounds initially present in non-irradiated syringes were destroyed by irradiation.     

Effect of Electron Beam Irradiation on the Properties of High Styrene Rubber/Styrene Butadiene Rubber Blends

High styrene rubber (HSR)/styrene butadiene rubber (SBR) blends at different ratios were exposed to various doses of electron beam irradiation. The effect of irradiation dose and blend ratios on the mechanical properties and shape memory characteristics in terms of strain fixation) rate (R_f) and strain recovery rate (R_r) was investigated. The results revealed that rich styrene blends displayed higher tensile strength and hardness than low styrene content blends at all irradiation doses. However, elongation at break, and toughness were lower for rich styrene content. Also, it was observed that for most specimens, the tensile strength, elongation at break and hardness increases up to100 kGy. Increasing irradiation doses resulted in slight deterioration in some mechanical properties only for low styrene content at150 kGy. According to the normalized tensile stress at 25% elongation, it was found that the contribution of irradiation in enhancing the mechanical properties is higher for rich butadiene blends. On the other hand, it was observed that rich styrene content blends possess higher R_f and R_r at all the irradiation doses and stretching temperatures. However, the increase of irradiation dose decreases R_f values; the extent of this decrease depends on the blend ratios. Conversely, for all blends, R_r were increased by increasing irradiation dose and styrene content ratios.     

Radiation degradation of polypropylene

Post-irradiation degradation of isotactic polypropylene irradiated by Co⁶⁰-γ-ray has been followed for 12 months. Effects of irradiation doses (10–100 kGy) up on the change of the structure and mechanical properties as well as flowability of this polymer has been studied. Carbonyl index increases with increasing post-irradiation time. The rate of which was much higher for doses above 50 kGy. Tensile strength declines with time and those samples irradiated above 50 kGy become quite brittle, just after irradiation. Results reveal that post-irradiation degradation of polypropylene irradiated by γ-ray occurs via chain scission mechanism.     

Evaluation of physico-chemical properties of electron beam-irradiated polycarbonate film

In this work, polycarbonate (PC) film samples were irradiated with 10 MeV electrons at different doses ranging from 25 to 250 kGy. Characterization techniques viz. thermogravimetric analysis (TGA), Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction analysis (XRD) and electron paramagnetic resonance (EPR) were exploited to understand the induced changes in the physico-chemical properties of the polymer. An increase in the decomposition temperature with increasing dose was observed, while the crystallinity remained unchanged as a result of the formation of cross-link bond. EPR technique characterized the stability of the free radicals in the irradiated PC. The result showed that cross-linking process occurs at low absorbed doses, whereas polymer degradation happens at higher doses.     

Effect of irradiation on thermal transitions in the siloxane block copolymer BCP 20 : 5

Thermal transitions in the 20: 5 polydimethylsiloxane (PDMS)-polyphenylsilsesquioxane block copolymer (BCP) and in PDMS subjected to γ-irradiation at doses to 100 kGy have been studied. It has been found that the release of a PDMS phase did not occur in the initial and irradiated BCPs. The irradiation of BCP with small doses leads to the formation of a significant amount of a gel fraction (to 25%) as a result of the grafting of cyclodimethylsiloxane (D_x) impurities to the PDMS block of the copolymer. This conclusion is supported by the results of thermal analysis and IR-spectroscopic data.     

Electron irradiation induced microstructural modifications in BaCl2 doped PVA: A positron annihilation study

Thin films of pure and 10 wt% BaCl₂ doped poly(vinyl alcohol) (PVA) were prepared by solution casting method. These films were subjected to electron irradiation for different doses ranging from 0 to 400 kGy in air at room temperature. The effect of electron irradiation on the optical and free volume related microstructures of these polymer films was studied using positron annihilation lifetime spectroscopy, FTIR and UV-vis techniques. The FTIR spectral studies indicate that the electron irradiation induces chemical modifications within the doped PVA, which results in chain scission as well as cross-linking of the polymer. The positron lifetime study on these irradiated polymers shows that the chain scissions and cross-linking within the polymer matrix affect the free volume content and hence the microstructure. The UV-vis optical absorption studies show that the induced microstructural change by electron irradiation also modifies the optical properties. Using UV-vis spectra, the optical energy band gap was estimated and it decreases with increase in electron dose. A correlation between positron results and optical results is obtained and electron irradiation induced microstructure modifications within the doped polymer are understood. The results highlight the usefulness of positron annihilation technique in the study of the microstructure of irradiated polymers.     

Use of some organic dyes in gamma irradiation dose determination

In the present work, the radiation-induced color bleaching of Remazol brilliant blue (RBB), Wegocet orange (WO), Methyl green (Me G) and Thioflavine S (Th S) dyes solutions was studied. Solutions of these dyes in different solvents were found to obey Beer’s law within certain concentration levels. The % color bleaching occurring in different dye solutions on using different gamma irradiation doses was determined and the data obtained showed the existence of good linear relationships among them in the four dye systems used. The linear sections lines were used as calibration curves for evaluating unknown gamma irradiation doses. From the obtained results, it was concluded that RBB in water, WO in ethanol, Me G in butanol and Th S in 60% ethanol–water mixture could be used for dose evaluation within the dose ranges 5–25 kGy for RBB, 20–90 kGy for WO, 10–70 kGy for Me G and 5–160 kGy for Th S. The sensitivity of the systems towards gamma radiations has been also reported.