Exploring the molecular reorientations in amorphous rosuvastatin calcium.

Molecular reorientations in rosuvastatin calcium, a drug that is widely used to prevent cardiovascular disease, were explored thoroughly by means of solid state nuclear magnetic resonance (1H and 13C NMR) combined with calculations of steric hindrances. The experimental results reveal rich internal reorientational dynamics. All relaxation processes were tested in a broad range of temperatures and described in terms of their type and the associated energy barriers. The internal molecular mobility of rosuvastatin calcium can be associated with the reorientational dynamics of four methyl groups, accompanied by reorientation of the isopropyl group. The energy barriers of methyl and isopropyl group reorientation depended on the type of E/Z isomers, while the water content also had a strong influence on the dynamics of the isopropyl group. In the paper, a consistent picture of the molecular dynamics is provided, facilitating our understanding of molecular mobility in this important pharmaceutical solid.

OPTICALLY STIMULATED LUMINESCENCE OF LiF:Mg,Cu,P POWDER-INFLUENCE OF THERMAL TREATMENT.

It was recently found that LiF:Mg,Cu,P, which is a very well-known thermoluminescent (TL) material, exhibits also quite substantial optically stimulated luminescence (OSL). In the present work a study on the influence of thermal treatment on the LiF:Mg,Cu,P OSL intensity has been performed. The results revealed that the well-known 'gold standard' of 240°C annealing is not appropriate for OSL measurements. The annealing at lower temperatures produced significantly higher OSL intensity. The highest enhancement of the OSL signal, reaching 95% (compared to the initial signal after standard annealing at 240°C/10 min) was obtained after annealing at about 190-200°C/30 min. The OSL emission spectrum of LiF:Mg,Cu,P was also measured and found to be peaked at 360 nm.

Optical and thermal pre-readout treatments to reduce the influence of fading on LiMgPO4 OSL measurements.

TL (Thermoluminescent) and OSL (Optically Stimulated Luminescence) techniques are both luminescent techniques widely applied in several areas into radiation dosimetry. The main difference between them are related to the employed stimulus (thermal or optical) for luminescent emission, as well as the advantages of each technique. Due to simplicity and not to be required heating, the OSL technique has been continuously improved and new researches in materials to be used with this technique have grown in the last decades. Nowadays the main problems in the application of the developed new materials are the poor stability and loss of OSL signal over time (fading). In this study, we performed a sequence of thermal (preheat) and optical (OSL with infra-red light stimulus) pre-readout treatments immediately before OSL readouts of LiMgPO4 based detectors (LMP), aiming the applicability of novel materials, contributing to find solutions to minimize the influence of fading. Moreover, it was demonstrated that the influence of fading is minimized and the stability of OSL signal from LMP is achieved using just optical process, without heating the material.

LITHIUM FLUORIDE CRYSTALS AS FLUORESCENT NUCLEAR TRACK DETECTORS.

Radiophotoluminescence signal of LiF crystals was found to be sufficiently strong to visualize tracks of a single charged particle. This was achieved with a wide-field fluorescent microscope equipped with a ×100 objective and LiF single crystals grown with the Czochralski method at IFJ PAN. The tracks of alpha particles, protons, as well as products of 6Li(n,α)3H reaction with thermal neutrons (moderated Pu/Be source), were observed. These encouraging results are the first steps towards practical use of LiF as fluorescent nuclear track detectors. The most promising dosimetric application seems to be neutron measurements.

IMAGING OF PROTON BRAGG PEAKS IN LiF.

Lithium fluoride (LiF) is one of the most common thermoluminescent phosphors routinely used in radiation protection services. Another advantageous property of LiF is radiophotoluminescence, whose occurs after its irradiation due to the creation of color centers. Excitation of LiF samples with a blue light causes the emission of photoluminescence, which spectrum consists of two peaks at ~520 and ~670 nm. The work was focused on imaging of Bragg peaks of proton beams routinely applied at the proton eye radiotherapy facility operating at the Institute of Nuclear Physics Polish Academy of Sciences (IFJ PAN) in Krakow by the measurement of the fluorescence light in LiF crystals excited with a 445 nm blue light after their previous irradiation with the proton beams of energies of 28, 30, 40 and 50 MeV. The range of proton beams in LiF crystals for different energies was calculated by Monte Carlo simulations.

Evaluation of the relative TL efficiency of the thermoluminescent detectors to heavy charged particles.

The relative thermoluminescence efficiency, η, is in general not constant but depends on ionisation density. Evaluation of the η is therefore important especially for correct interpretation of measurements of densely ionising radiation doses in proton radiotherapy or in space dosimetry. The correct determination of the η is not always straightforward especially when more strongly ionising radiation is to be measured. In the present work, the process of calculation of the η based on two kinds of heavy charged particles was studied. Several factors which may influence the value of the η and their significance for the final result were discussed. These include for example non-uniform deposition of the dose within the detector volume, self-attenuation of thermoluminescent light, choice of the reference radiation, etc. The presented approach was applied to the experimental results of η of LiF:Mg,Ti detectors irradiated with two kinds of heavy charged particles, protons and alpha particles.

Phase diagram of water confined in MCM-41 up to 700 MPa.

On the basis of measurements of NMR signal intensity and T1 and T2(*) relaxation times as a function of temperature (290 K-170 K) and pressure (0.1 MPa-700 MPa), the p-T phase diagram was made for the sample containing water inside and outside MCM-41 pores of 1.81 nm in radius. The temperature of nucleation of water confined in nanopores under normal pressure was 230 K. With increasing pressure this temperature decreased to 200 K under 300 MPa, but with further increase in pressure it did not change.

Relative TL and OSL efficiency to protons of various dosimetric materials.

Thermoluminescence (TL) and optically stimulated luminescence (OSL) are the well-known phenomena used for passive methods of dose measurements. TL and OSL detectors are frequently used in the dosimetry of cosmic radiation in space and of particle radiotherapy beams. However, the relative TL/OSL efficiency, which is defined as a ratio of the emitted light intensity per unit dose for a given radiation type, to the same quantity for the reference gamma radiation is not constant and depends on radiation type and energy. In the present work several types of TL and OSL dosimetric materials, including lithium fluoride (LiF), aluminium oxide, beryllium oxide and lithium aluminate, were tested with protons. The measurements were realised exploiting the 60-MeV proton beam of the AIC-144 cyclotron in the Proton Eye Radiotherapy Facility at Institute of Nuclear Physics (IFJ PAN). The influence of proton energy on the relative efficiency and other TL/OSL characteristics of the studied detector types was presented.

Alpha particle and proton relative thermoluminescence efficiencies in LiF:Mg,Cu,P:is track structure theory up to the task?

Low-energy alpha particle and proton heavy charged particle (HCP) relative thermoluminescence (TL) efficiencies are calculated for the major dosimetric glow peak in LiF:Mg,Cu,P (MCP-N) in the framework of track structure theory (TST). The calculations employ previously published TRIPOS-E Monte Carlo track segment values of the radial dose in condensed phase LiF calculated at the Instituto National de Investigaciones Nucleares (Mexico) and experimentally measured normalised (60)Co gamma-induced TL dose-response functions, f(D), carried out at the Institute of Nuclear Physics (Poland). The motivation for the calculations is to test the validity of TST in a TL system in which f(D) is not supralinear (f(D) >1) and is not significantly dependent on photon energy contrary to the behaviour of the dose-response of composite peak 5 in the glow curve of LiF:Mg,Ti (TLD-100). The calculated HCP relative efficiencies in LiF:MCP-N are 23-87% lower than the experimentally measured values, indicating a weakness in the major premise of TST which exclusively relates HCP effects to the radiation action of the secondary electrons liberated by the HCP slowing down. However, an analysis of the uncertainties involved in the TST calculations and experiments (i.e. experimental measurement of f(D) at high levels of dose, sample light self-absorption and accuracy in the estimation of D(r), especially towards the end of the HCP track) indicate that these may be too large to enable a definite conclusion. More accurate estimation of sample light self-absorption, improved measurements of f(D) and full-track Monte Carlo calculations of D(r) incorporating improvements of the low-energy electron transport are indicated in order to reduce uncertainties and enable a final conclusion.

Eye lens dosimetry: task 2 within the ORAMED project.

The ORAMED (Optimization of RAdiation protection for MEDical staff) project is funded by EU-EURATOM within the 7° Framework Programme. Task 2 of the project is devoted to study the dose to the eye lens. The study was subdivided into various topics, starting from a critical revision of the operational quantity H(p)(3), with the corresponding proposal of a cylindrical phantom simulating as best as possible the head in which the eyes are located, the production of a complete set of air kerma to dose equivalent conversion coefficients for photons from 10 keV to 10 MeV, and finally, the optimisation of the design of a personal dosemeter well suited to respond in terms of H(p)(3). The paper presents some preliminary results.

NMR search for polymorphic phase transformations in chlorpropamide form-A at high pressures.

The high-pressure effects on chlorpropamide (C10H13ClN2O3S) form-A have been studied by 1H NMR spectroscopy at high pressures up to 800 MPa in the temperature range 90-300 K. A study of the NMR second moment and spin-lattice relaxation time has been completed by a calculation of the steric hindrances for molecular reorientations and simulations of the second moment of the NMR line by the Monte-Carlo method, which enabled a precise description of molecular dynamics in the compound studied. Reorientations of the methyl group, oscillations and reorientations of the chlorophenyl ring and reorientations of the propyl group have been revealed and respective activation parameters extracted. No phase transformation of the compound form-A has been detected.

Validation of modelling the radiation exposure due to solar particle events at aircraft altitudes.

Dose assessment procedures for cosmic radiation exposure of aircraft crew have been introduced in most European countries in accordance with the corresponding European directive and national regulations. However, the radiation exposure due to solar particle events is still a matter of scientific research. Here we describe the European research project CONRAD, WP6, Subgroup-B, about the current status of available solar storm measurements and existing models for dose estimation at flight altitudes during solar particle events leading to ground level enhancement (GLE). Three models for the numerical dose estimation during GLEs are discussed. Some of the models agree with limited experimental data reasonably well. Analysis of GLEs during geomagnetically disturbed conditions is still complex and time consuming. Currently available solar particle event models can disagree with each other by an order of magnitude. Further research and verification by on-board measurements is still needed.

Oxidation of flame retardant tetrabromobisphenol A by singlet oxygen.

Wide use of flame retardants can pose an environmental hazard, and it is of interest to investigate how they may degrade. We report here that 3,3',5,5'-tetrabromobisphenol A (TBBPA) is subject to photosensitized oxidation involving singlet molecular oxygen ((1)O2). By using visible light and rose bengal or methylene blue as 102 photosensitizers, we have found that TBBPA is a 102 quencher. The quenching rate constant, k(q), depends on TBBPA ionization (pK = 7.4). In acetonitrile, where TBBPA is undissociated, the kq value is 6.1 x 10(5) M(-1) s(-1) for a TBBPA monomer and decreases to 2.9 x 10(4) M(-1) s(-1) for TBBPA dimers and/or aggregates. TBBPA dissociates in aqueous solutions, and its kq value is 1.44 x 10(9) M(-1) s(-1) in alkaline solution, decreasing to 3.9 x 10(8) M(-1) s(-1) at pH 7.2. The strong 102 quenching by TBBPA anion initiates an efficient oxidation of TBBPA, which results in oxygen consumption in aqueous micellar (e.g., Triton X-100) solutions containing photosensitizer. This oxygen consumption is mediated by transient radical species, which we detected by using EPR spectroscopy. We observed two major radicals and one minor radical generated from TBBPA by reaction with 102 at pH 10. One was identified as the 2,6-dibromo-p-benzosemiquinone radical (a2H = 2.36 G, g = 2.0056). A second radical (aH = 2.10 G, g = 2.0055) could not be identified butwas probably a 2,6-dibromo-p-benzosemiquinone radical containing an EPR-silent substituent at the 3-position. Spin trapping with 5,5-dimethyl-1-pyrroline N-oxide (DPMO) showed that other minor radicals (hydroxyl, carbon-centered) are also generated during the reaction of TBBPA with (1)O2. The photosensitized production of radicals and oxygen consumption were completely inhibited by the azide anion, an efficient physical (1)O2 quencher. Because TBBPA is a stable compound that at neutral pH does not absorb much of the atmosphere-filtered solar radiation, its photosensitized oxidation by (1)O2 may be the key reaction initiating or mediating TBBPA degradation in the natural environment.

The problems associated with the monitoring of complex workplace radiation fields at European high-energy accelerators and thermonuclear fusion facilities.

The European Commission is funding within its Sixth Framework Programme a three-year project (2005-2007) called CONRAD, COordinated Network for RAdiation Dosimetry. The organisational framework for this project is provided by the European Radiation Dosimetry Group EURADOS. One task within the CONRAD project, Work Package 6 (WP6), was to provide a report outlining research needs and research activities within Europe to develop new and improved methods and techniques for the characterisation of complex radiation fields at workplaces around high-energy accelerators, but also at the next generation of thermonuclear fusion facilities. The paper provides an overview of the report, which will be available as CERN Yellow Report.

Dosimetric properties of new cards with high-sensitivity MCP-N (LiF:Mg,Cu,P) detectors for Harshaw automatic reader.

A new configuration for a thermoluminescent dosimetric card has been developed through collaboration between the Institute of Nuclear Physics in Kraków and several commercial dosimetric companies. The card is based on high-sensitivity LiF:Mg,Cu,P circular pellets (MCP-N) welded inside synthetic foils. The basic configuration consists of two pellets of 3.6 mm diameter and thicknesses from 0.25 up to 0.38 mm. The cards can be processed in a standard 6600 or 8800 Harshaw automatic TLD reader. The dosemeters demonstrate very high sensitivity, low background and good stability. This article presents results of the performance tests of the new dosimetric cards in the automatic TLD readers and a comparison of their properties.

Photochemistry and photocytotoxicity of alkaloids from Goldenseal (Hydrastis canadensis L.). 2. Palmatine, hydrastine, canadine, and hydrastinine.

Goldenseal is an herb that is widely used in dietary supplements, eye washes, and skin lotions. The presence of Goldenseal root powder in dietary supplements and the topical application of Goldenseal preparations raise the possibility that an adverse phototoxic reaction may result from an interaction between its constituent alkaloids and light in exposed tissues. We have previously shown that berberine, the major alkaloid in Goldenseal powder, in combination with UVA causes DNA damage and cell death in HaCaT keratinocytes [(2001) Chem. Res. Toxicol. 14, 1529]. We have studied the photochemical and photobiological properties of four minor alkaloids found in Goldenseal, namely, hydrastine, palmatine, canadine, and hydrastinine. UVA radiation of palmatine in aqueous solutions generated no (1)O(2), but in CH(2)Cl(2), copious amounts of (1)O(2) were detected (Phi = 0.2). Palmatine also photogenerated oxygen-centered radicals, (*)OH and O(2)(*)(-) in aerated aqueous buffer and acetonitrile, respectively, as detected by the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO). In nitrogen-sparged acetonitrile containing DMPO, we observed the neutral palmatine radical formed by one-electron reduction. UVA irradiation (4 J/cm(2)) of HaCaT keratinocytes in the presence of palmatine (50 microM) resulted in a 50% decrease in cell viability but no DNA damage as measured by the comet assay. UVA irradiation of hydrastine, hydrastinine, or canadine (50 microM) did not cause DNA damage or cell death in keratinocytes. Although palmatine is photoactive, it is present in such small amounts in Goldenseal root powder that the phototoxicity of the herb is most likely due to berberine, the major constituent alkaloid.

Dosimetry of densely ionising radiation with three LiF phosphors for space applications.

A new method of thermoluminescence dosimetry of densely ionising radiation based on the ratio of different efficiency-LET functions of three thermoluminescent detectors (TLDs) has been developed. The applied TLD types are: MTS-7 ((7)LiF:Mg,Ti), MCP-7 ((7)LiF:Mg,Cu,P) and MTT-7 (a newly developed (7)LiF:Mg,Ti with modified activator composition and increased response to high-LET radiation). The tests of this method, performed with high-energy ion beams at the HIMAC accelerator within the ICCHIBAN project, proved that good agreement with the true dose values may be achieved even in very complicated mixed fields. The proposed method will be applied for analysis of several thousand TLDs used for the determination of organ doses in an anthropomorphic phantom orbiting outside the International Space Station within the MATROSHKA experiment.

Application of different TL detectors for the photon dosimetry in mixed radiation fields used for BNCT.

Different approaches for the measurement of a relatively small gamma dose in strong fields of thermal and epithermal neutrons as used for Boron Neutron Capture Therapy (BNCT) have been studied with various thermoluminescence detectors (TLDs). CaF(2):Tm detectors are insensitive to thermal neutrons but not tissue-equivalent. A disadvantage of applying tissue-equivalent (7)LiF detectors is a strong neutron signal resulting from the unavoidable presence of (6)Li traces. To overcome this problem it is usual to apply pairs of LiF detectors with different (6)Li content. The experimental determination of the thermal neutron response ratio of such a pair at the Geesthacht Neutron Facility (GeNF) operated by PTB enables measurement of the photon dose. In the experimental mixed field of thermal neutrons and photons of the TRIGA reactor at Mainz the photon dose measured with different types of (7)LiF/(nat)LiF TLD pairs agree within a standard uncertainty of 6% whereas the CaF(2):Tm detectors exhibit a photon dose by more than a factor of 2 higher. It is proposed to determine suitable photon energy correction factors for CaF(2):Tm detectors with the help of the (7)LiF/(nat)LiF TLD pairs in the radiation field of interest.

On the dose response of some CVD diamond thermoluminescent detectors.

The linearity of dose response of chemical vapour deposition (CVD) diamonds grown at the Institute for Materials Research at Limburg University, Belgium, was investigated over a dose range relevant for radiotherapy. The following CVD diamonds were investigated: (1) a batch of square 3 x 3 mm2 detectors cut from a CVD wafer and (2) an as-grown CVD wafer of 6 cm diameter. A total of 20 CVD square detectors were irradiated with 137Cs gamma rays over the dose range from 200 mGy to 25 Gy. The CVD wafer, used as a large-area thermoluminescent (TL) detector, was exposed to a 226Ra needle. Very few square detectors showed linearity over a limited dose range, followed by saturation of the TL signal. The dose range of linearity was found to be strongly affected by the thermal annealing procedure of the detector. Owing to its high sensitivity and homogeneity of response, the large CVD diamond wafer was found to be very suitable as a large-area detector for 2-D dose mapping of the 226Ra brachytherapy source, possibly for Quality Assurance purposes.