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P Bilski

Publications and source records attributed to P Bilski.

At least 37 records · Page 2Linked to original sources

Lithium fluoride: from LiF:Mg,Ti to LiF:Mg,Cu,P.

Differences and similarities between LiF-based LiF:Mg,Ti and LiF:Mg,Cu,P are discussed, with respect to their dosimetric properties--sensitivity, non-linearity of dose response and heavy charged particle efficiency, as related to the concentration and the individual role of the Mg, Ti, Cu and P dopants. To study further the role of these dopants, the properties of some new, 'hybrid' phosphors: LiF:Mg,Cu,Ti and LiF:Mg,P, specially developed for this purpose, are also discussed. In the glow curve of LiF:Mg,Cu,P with a low concentration of Mg a new peak was found, which appears to be an analogue of peak 4 in LiF:Mg,Ti, Magnesium apparently controls most of the dosimetric properties of LiF-based phosphors. For instance, charged-particle efficiency appears to be anti-correlated with the concentration of Mg, being much less dependent on the content of other dopants. On the other hand, some properties of LiF-based systems seem to be correlated with changes in the emission spectra. It is suggested that Ti hampers the acceptance of any increased amount of Mg into more traps in LiF:MgTi. The absence of Ti, not the presence of P or Cu, is therefore a key to the high sensitivity of LiF:MgCuP.

Copper↗

Characterisation of thermoluminescent LiF:Mg,Ti (MTS-N) detectors in the 85-550 K temperature range.

Miniature LiF:Mg,Ti (MTS-N) pellets, specially designed for dosimetry in proton radiotherapy, were studied in the 85-550 K temperature range. TL glow curves for differently Mg- or Ti-doped detectors were recorded, showing the preponderant influence of Mg concentration on the intensity of peak 5. The presence of a three-peak complex was also confirmed near 140 K; spectral emission of this peak consists of two bands whose maxima occur at 290 and 420 nm. TSEE glow curves above 300 K similar to those of TL were observed. The behaviour of TSEE and TL peak 5 following an X ray exposure from 33 to 500 Gy was studied: its intensity is a linear function of air kerma in both cases.

Fluorides↗

TL emission spectra from differently doped LiF:Mg detectors.

There are two widely applied types of thermoluminescent detectors based on LiF:Mg luminophor: Lif:Mg,Ti and highly sensitive LiF:Mg,Cu,P. The role of luminescence centres in these materials is usually attributed to defects connected with, respectively, titanium and phosphorus dopants. In order to check how composition of dopants introduced into the LiF lattice influences emission spectra, measurements on a series of variously doped LiF:Mg samples were performed. Apart from LiF:Mg,Cu,P and LiF:Mg,Ti detectors with different concentration of activators, an experimental sample being a kind of a 'hybrid' between both standard materials was also prepared. It was synthesised with concentrations of magnesium and copper identical to those used for LiF:Mg,Cu,P preparation. but instead of phosphorus it was doped with titanium (LiF:Mg,Cu,Ti). The measurements of the emission spectra were performed by using a liquid nitrogen cooled CCD 1024E detector with an SP150 spectrograph. During the measurements the samples were placed inside a cryostat in a vacuum. Resulting data were numerically deconvoluted for individual peaks with respect to the wavelength and the temperature. The glow curve shape of this material resembles that of LiF:Mg,Cu,P, while sensitivity is at the level of LiF:Mg,Ti. Preliminary results indicate that emission of the LiF:Mg,Cu,Ti sample is similar to that of LiF:Mg,Cu,P rather than to LiF:Mg,Ti, showing a maximum for wavelengths well below 400 nm.

Copper↗

Investigation of radiation doses in open space using TLD detectors.

The low energy component of the cosmic radiation field is strongly modified by the shielding of the spacecraft and it is time and location dependent. Thermoluminescent lithium fluoride detectors have been applied to determine the radiation doses inside the ESA-Facility BIOPAN. The BIOPAN facility was mounted outside and launched on a Foton spacecraft and opened to space to allow exposure of several experiments to open space. Standard TLD-600. TLD-700 chips, two layers MTS-Ns sintered pellets with different effective thickness of the sensitive layer and MTS-N of different thickness have been exposed with different shielding thicknesses in front of them. The measured TL signal in the 0.1 mm thick detector just shielded by an aluminised Kapton foil of 25 microm thickness in front yielded a dose of 29.8 Gy (calibrated with 137Cs gamma rays) for an exposure time of 12.7 days: after 2.5 g.cm(-2) shielding the doses dropped to 3 mGy. The monitoring of radiation doses and its depth dose distribution outside the spacecraft are of great interest for radiation protection of astronauts working in open space. The knowledge of depth-dose distribution is a prerequisite to determine the organ doses an astronaut will receive during an extravehicular activity (EVA). The BIOPAN experiments are to be continued in the future.

Aerospace Medicine↗

Response of TL dosemeters to cosmic radiation on board passenger aircraft.

Measurements were performed with various LiF based TLDs on board seven Polish aircraft, flying long-distance or middle-distance routes. All of the 7LiF detectors used (various types of 7LiF:Mg,Ti and 7LiF:Mg,Cu,P detectors), which measure the non-neutron component of the radiation field, produced consistent results. It was found that the characteristics of the TLD response (ratio of different detector responses, glow curve shapes) after doses of radiation at flying altitudes differ from those obtained after exposure at the CERN facility (CERF), suggesting a lower contribution of densely ionising radiation. The neutron induced TL signal was also more affected by the thickness of the holder, suggesting the presence of a softer neutron energy spectrum at flight altitudes. Further in-flight and CERF exposures of detectors are planned to resolve these issues.

Aerospace Medicine↗

Miniature thermoluminescent detectors for dosimetry in radiotherapy.

At the Institute of Nuclear Physics in Kraków (INP), in collaboration with the Centre of Oncology in Kraków, several types of miniature thermoluminescent LiF:Mg,Ti and LiF:Mg,Cu,P detectors specially designed for clinical dosimetry in radiotherapy have been developed. The detectors are manufactured in the form of solid pellets of diameter down to 1 mm and typical thickness 0.5 mm, in the form of rods with a diameter of 0.5 mm and a length of a few mm, and as two-layer detectors with a thin (in the range of 0.065 mm) active layer of high-sensitive LiF:Mg,Cu,P. All three types of newly developed detectors have already been applied in proton beam dosimetry, surface dosimetry of eye-plaque brachytherapy applicators, phantom dosimetry for vascular brachytherapy and in vivo dosimetry in interstitial brachytherapy. These detectors were found to be very useful for dose measurements in high dose gradients, where spatial resolution better than 1 mm is required.

Brachytherapy↗

Validation of a radiotherapy treatment planning system using an anthropomorphic phantom and MTS-N thermoluminescent detectors.

A treatment planning system (TPS) was validated in conditions of simulated radiotherapy (RT) of an anthropomorphic tissue-equivalent phantom. Individually calibrated solid MTS-N (LiF:Mg,Ti) detectors were placed within the treatment volume in this phantom which was then repeatedly irradiated by external 60Co or 6 MV X ray beams. On the basis of TLD-measured depth-dose curves for the two beams, the relative accuracy of determining dose (of the order of 1 Gy) at live depths in a water phantom is about 0.4-0.6%. In the volume of interest representing the target volume, the relative standard difference between the calculated and measured dose values ranged between 1.3% and 2.2% for the 60Co and 6 MV X ray beams, respectively. The TPS-calculated uniformity of irradiation of that volume is within 1%. While fraction-to-fraction repeatability was within 1-2%, systematic underexposure around the reference point, by 2-3%, was found in two consecutive exposures by sets of both beams.

Absorption↗

Photochemistry and photocytotoxicity of alkaloids from Goldenseal (Hydrastis canadensis L.) 1. Berberine.

Goldenseal is an herb which is widely used for many medical applications such as in eyewashes and skin lotions and which is currently undergoing testing by the National Toxicology Program. The main alkaloid constituent of Goldenseal is berberine. The topical application of Goldenseal or berberine to the skin or eyes raises the possibility that an adverse phototoxic reaction may result from an interaction between the alkaloid and light. We have therefore studied the photochemistry of berberine in different solvents and its phototoxicty to HaCaT keratinocytes. Irradiation of berberine in aqueous solutions does not generate (1)O(2), but in CH(2)Cl(2), (1)O(2) is produced with a quantum yield phi = 0.34. With the aid of the electron paramagnetic resonance (EPR) spin trapping technique and 5,5-dimethyl-1-pyrroline N-oxide (DMPO), we have detected oxygen-centered radicals photogenerated by berberine in water and acetonitrile. In the latter solvent and in the absence of oxygen, the neutral berberine radical formed by one electron reduction was observed. Methanol radicals were detected by EPR in water/alcohol low-temperature glasses irradiated in the berberine long-wavelength absorption band. In such alcoholic glasses, we have also detected an EPR signal from the berberine triplet at 77 K, in contrast to aqueous glasses where neither triplet nor radicals were detectable. Our data show that, although a weak photosensitizer in water, berberine is able to produce both (1)O(2) and radical species in a nonpolar environment. UVA irradiation of HaCaT keratinocytes in the presence of 50 microM berberine resulted in an 80% decrease in cell viability and a 3-fold increase in DNA damage as measured by the Comet assay. These findings suggest that exposure to sunlight or artificial light sources emitting UVA should be avoided when topical preparations derived from Goldenseal or containing berberine are used.

Administration, Topical↗

Dosimetry of low-energy protons and light ions.

For the vertical beam facility at the 14 MV Munich tandem accelerator, various techniques for dosimetry were tested for radiation fields of low-energy protons and light ions (4He, 12C and 16O). A reference dose was determined from the fluence of particles by counting individual particles. A parallel-plate Markus chamber with a small sensitive air volume was used for beam dosimetry applying the ICRU protocol. The doses measured with the ionization chamber were compared with doses evaluated from the fluence measurements. Alternative dose measurements were performed using MTS-N LiF:Mg, Ti thermoluminescence detectors (TLDs) and a photometrically evaluated Fricke chemical dosimeter. An uncertainty of 8% was found in the determination of the dose relative to the reference method. Effects of an inhomogeneous energy loss and a finite track length of the projectiles in the sensitive detector volume of the dosimeters had to be taken into account.

Biophysical Phenomena↗

Quenching of singlet molecular oxygen (1O2) by azide anion in solvent mixtures.

The azide ion is a strong physical quencher of singlet molecular oxygen (1O2) and is frequently employed to show involvement of 1O2 in oxidation processes. Rate constants (k(q)) for the quenching of 1O2 by azide are routinely used as standards to calculate k(q) values for quenching by other substrates. We have measured k(q) for azide in solvent mixtures containing deuterium oxide (D2O), acetonitrile (MeCN), 1,4-dioxane, ethanol (EtOH), propylene carbonate (PC), or ethylene carbonate (EC), mixtures commonly used for many experimental studies. The rate constants were calculated directly from 1O2 phosphorescence lifetimes observed after laser pulse excitation of rose bengal (RB), used to generate 1O2. In aqueous mixtures with MeCN and carbonates, the rate constant increased nonlinearly with increasing volume of organic solvent in the mixtures. k(q) was 4.78 x 10(8) M(-1) s(-1) in D2O and increased to 26.7 x 10(8) and 27.7 x 10(8) M(-1) s(-1) in 96% MeCN and 97.7% EC/PC, respectively. However, in EtOH/D2O mixtures, k(q) decreased with increasing alcohol concentration. This shows that a higher solvent polarity increases the quenching efficiency, which is unexpectedly decreased by the proticity of aqueous and alcohol solvent mixtures. The rate constant values increased with increasing temperature, yielding a quenching activation energy of 11.3 kJ mol(-1) in D2O. Our results show that rate constants in most solvent mixtures cannot be derived reliably from k(q) values measured in pure solvents by using a simple additivity rule. We have measured the rate constants with high accuracy, and they may serve as a reliable reference to calculate unknown k(q) values.

Journal Article↗

Dosimetry of low-energy protons on the vertical-beam facility at the Munich accelerator.

Various methods of dosimetry for protons with energies up to 25 MeV were compared for radiation fields as might be used in the skin treatment of patients or in biological experiments. The methods used were: Fluence of individually registered protons; Charge deposition in commercially available ionisation chambers; Thermoluminescence detectors, exposed in Munich and evaluated in Krakow; Photometricallly evaluated commercial Fricke dosimeter. An overall agreement within 5% was found between the absolute dose measurements. Depth-dose distributions for Bragg curves measured by a Markus chamber with a depth resolution of 10 micrometers agreed with calculations.

Ferrous Compounds↗

Biological effects of menadione photochemistry: effects of menadione on biological systems may not involve classical oxidant production.

Because cell-mediated reduction of menadione leads to the generation of reactive oxygen species (ROS), this quinone is widely used to investigate the effects of ROS on cellular functions. We report that A549 human lung epithelial cells exposed to menadione demonstrate a dose-dependent increase in both intracellular calcium ([Ca(2+)](i)) and ROS formation. The concentrations of menadione required to initiate these two events are markedly different, with ROS detection requiring higher levels of menadione. Modulators of antioxidant defences (e.g. buthionine sulphoximine, 3-amino-1,2,4-triazole) have little effect on the [Ca(2+)](i) response to menadione, suggesting that ROS formation does not account for menadione-dependent alterations in [Ca(2+)](i). Additional evidence suggests that menadione photochemistry may be responsible for the observed [Ca(2+)](i) effects. Specifically: (a) EPR studies with the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) show that light exposure (maximum effect at 340 nm) stimulates menadione-dependent formation of the DMPO/(.)OH spin adduct that was not sensitive to antioxidant interventions; (b) DMPO inhibits menadione and light-dependent increases in [Ca(2+)](i); and (c) light (maximum effect at 340 nm) augments the deleterious effects of menadione on cell viability as determined by (51)Cr release. These photo effects do not appear to involve formation of singlet oxygen by menadione, but rather are the result of the oxidizing chemistry initiated by menadione in the triplet state. This work demonstrates that menadione species generated by photo-irradiation can exert biological effects on cellular functions and points to the potential importance of photochemistry in studies of menadione-mediated cell damage.

Calcium↗

Vitamin B6 (pyridoxine) and its derivatives are efficient singlet oxygen quenchers and potential fungal antioxidants.

Vitamin B6 (pyridoxine, 1) and its derivatives: pyridoxal (2), pyridoxal 5-phosphate (3) and pyridoxamine (4) are important natural compounds involved in numerous biological functions. Pyridoxine appears to play a role in the resistance of the filamentous fungus Cercospora nicotianae to its own abundantly produced strong photosensitizer of singlet molecular oxygen (1O2), cercosporin. We measured the rate constants (kq) for the quenching of 1O2 phosphorescence by 1-4 in D2O. The respective total (physical and chemical quenching) kq values are: 5.5 x 10(7) M-1 s-1 for 1; 7.5 x 10(7) M-1 s-1 for 2, 6.2 x 10(7) M-1 s-1 for 3 and 7.5 x 10(7) M-1 s-1 for 4, all measured at pD 6.2. The quenching efficacy increased up to five times in alkaline solutions and decreased approximately 10 times in ethanol. Significant contribution to total quenching by chemical reaction(s) is suggested by the degradation of all the vitamin derivatives by 1O2, which was observed as declining absorption of the pyridoxine moiety upon aerobic irradiation of RB used to photosensitize 1O2. This photodegradation was completely stopped by azide, a known physical quencher of 1O2. The pyridoxine moiety can also function as a redox quencher for excited cercosporin by forming the cercosporin radical anion, as observed by electron paramagnetic resonance. All B6 vitamers fluoresce upon UV excitation. Compounds 1 and 4 emit fluorescence at 400 nm, compound 2 at 450 nm and compound 3 at 550 nm. The fluorescence intensity of 3 increased approximately 10 times in organic solvents such as ethanol and 1,2-propanediol compared to aqueous solutions, suggesting that fluorescence may be used to image the distribution of 1-4 in Cercospora to understand better the interactions of pyridoxine and 1O2 in the living fungus.

Ascomycota↗

Dihydrocercosporin singlet oxygen production and subcellular localization: a possible defense against cercosporin phototoxicity in Cercospora.

Fungi in the genus Cercospora produce cercosporin, a potent singlet oxygen (1O2)-generating photosensitizer that plays a critical role in the ability of these fungi to parasitize plants. Although plants, mice, bacteria and many fungi are sensitive to cercosporin, Cercospora species are resistant to its toxicity. The cellular resistance of these fungi to cercosporin has been correlated with fungal cell surface reducing ability and the ability to maintain cercosporin in a chemically reduced state. As a model for reduced cercosporin we employed a reduced, acetylated derivative (hexaacetyl-dihydrocercosporin, HAC) that we tested for 1O2 production in a range of solvents. We found that as a 1O2 photosensitizer, HAC was only moderately effective in organic solvents (phi SO = 0.14-0.18) and very poor in water (phi SO = 0.02-0.04). By contrast, the 1O2 quantum yield of cercosporin itself was unaffected by solvent (phi SO = 0.84-0.97). To investigate the localization of reduced cercosporin in fungal cells, we developed a fluorescence assay using laser scanning confocal microscopy. This assay showed a uniform green fluorescence, indicative of reduced cercosporin, in the cytoplasm of hyphal cells treated with cercosporin. We hypothesize that the main protection mechanism against cercosporin phototoxicity in the fungus consists of transformation of cercosporin to a reduced state and localization of this reduced form in the aqueous compartment of the cell, thus decreasing intracellular 1O2 production to levels that can be tolerated by the fungus. In addition, we have, for the first time, directly detected 1O2 phosphorescence from fungal culture, either stained with the photosensitizer rose bengal or actively synthesizing cercosporin, demonstrating 1O2 production in vivo and from cercosporin in culture.

Animals↗

A highly conserved sequence is a novel gene involved in de novo vitamin B6 biosynthesis.

The Cercospora nicotianae SOR1 (singlet oxygen resistance) gene was identified previously as a gene involved in resistance of this fungus to singlet-oxygen-generating phototoxins. Although homologues to SOR1 occur in organisms in four kingdoms and encode one of the most highly conserved proteins yet identified, the precise function of this protein has, until now, remained unknown. We show that SOR1 is essential in pyridoxine (vitamin B6) synthesis in C. nicotianae and Aspergillus flavus, although it shows no homology to previously identified pyridoxine synthesis genes identified in Escherichia coli. Sequence database analysis demonstrated that organisms encode either SOR1 or E. coli pyridoxine biosynthesis genes, but not both, suggesting that there are two divergent pathways for de novo pyridoxine biosynthesis in nature. Pathway divergence appears to have occurred during the evolution of the eubacteria. We also present data showing that pyridoxine quenches singlet oxygen at a rate comparable to that of vitamins C and E, two of the most highly efficient biological antioxidants, suggesting a previously unknown role for pyridoxine in active oxygen resistance.

Animals↗

Merocyanine 540 solubilized as an ion pair with cationic surfactant in nonpolar solvents: spectral and photochemical properties.

Merocyanine 540 (MC) is an anionic dye that is used to photopurge the bone marrow of leukemia cells. Under these conditions it is localized mostly in cell membranes, which may affect its photochemical reactivity. We investigated the photochemistry of MC dissolved as a hydrophobic ion pair with a hexadecyltrioctadecylammonium cation in cyclohexane, trimethylpentane and toluene as well as in propylene carbonate, CH3CN, C2H5OH and D2O. In organic solvents, the absorption and fluorescence spectra of MC were strongly red-shifted compared with aqueous solutions. The fluorescence was also more intense despite aggregation that occurred in some solvents. Aggregation strongly affects the spectral and photochemical properties of MC, especially in aliphatic hydrocarbons in which distinctive H-type aggregates are formed. Hydrophobic MC is a moderate photosensitizer of singlet molecular oxygen (1O2). The following values for 1O2 quantum yields were calculated based on 1O2 phosphorescence relative to 1O2 generation by Rose Bengal: approximately 0.12 in trimethylpenthane, approximately 0.13 in cyclohexane, 0.045 in EtOH, 0.039 in toluene, 0.007 in CH3CN and approximately 3 x 10(-4) in D2O. The H-aggregates of MC in cyclohexane and trimethylpentane are better 1O2 producers than monomeric MC. The above 1O2 quantum yields are corrected for self-quenching because MC is an efficient 1O2 quencher (17 x 10(7) M-1 s-1 in CH3CN, 6.8 x 10(7) M-1 s-1 in D2O, 5.2 x 10(7) M-1 s-1 in EtOH, and 1.4 x 10(7) M-1 s-1 in toluene). Merocyanine undergoes photodegradation, a solvent-dependent process that proceeds faster when the dye is aggregated. The initial photodegradation rate is much slower in organic solvents than in water, but photodegradation products accumulated during longer irradiation may increase the rate in most solvents. Higher photostability and better photosensitization by MC in hydrophobic nonpolar solvents suggest that the killing of leukemia cells via a photodynamic mechanism may operate mostly in cell membranes. In contrast, any cytotoxic products from photodecomposition may be important in hydrophilic cell compartments. Our data show the spectral and photochemical properties of MC in a pure hydrophobic environment.

Humans↗

Influence of solvent polarity and proticity on the photochemical properties of norfloxacin.

The fluoroquinolone antibacterial norfloxacin (NF) is a moderate photosensitizer of singlet molecular oxygen (1O2). We have studied photosensitization by NF as a function of medium polarity and proticity in solvent mixtures. We have used 1,4-dioxane and propylene carbonate mixtures to keep proticity constant while modulating polarity, and water/D2O and ethylene carbonate mixtures to alter proticity without large changes in polarity. The absorption spectrum of NF was little affected by solvent changes, as compared to the fluorescence spectrum that exhibited as much as a 50 nm blue-shift, e.g. 1,4-dioxane versus D2O. The quantum yield of NF fluorescence saturated at an almost 10 times higher value (approximately 0.14) when proticity was increased by added water, up to 0.2 mol fraction, to ethylene carbonate. Less pronounced, the increasing polarity in 1,4-dioxane/propylene carbonate mixtures affected the fluorescence yield much less. Norfloxacin produces 1O2 and is able to quench 1O2. The rate constant for 1O2 quenching is 4.5 x 10(7) M-1 s-1 in propylene carbonate but decreases ca four times in D2O. The quantum yield of 1O2 photogeneration was also up to five times higher in solvents that were both protic and polar than vice versa. Our data show that NF is more photochemically active in an environment that is both protic and polar. This suggests the involvement of polar excited state(s) and possible proton/hydrogen transfer during photoexcitation. Similar processes may initiate the phototoxic response reported in some patients treated with the fluoroquinolone drugs. The phototoxicity of NF and other fluoroquinolone antibiotics may strongly depend on their localization in hydrophilic or hydrophobic cell/tissue regions.

Animals↗