Accuracy of dose planning for prostate radiotherapy in the presence of metallic implants evaluated by electron spin resonance dosimetry

Radiotherapy is one of the main approaches to cure prostate cancer, and its success depends on the accuracy of dose planning. A complicating factor is the presence of a metallic prosthesis in the femur and pelvis, which is becoming more common in elderly populations. The goal of this work was to perform dose measurements to check the accuracy of radiotherapy treatment planning under these complicated conditions. To accomplish this, a scale phantom of an adult pelvic region was used with alanine dosimeters inserted in the prostate region. This phantom was irradiated according to the planned treatment under the following three conditions: with two metallic prostheses in the region of the femur head, with only one prosthesis, and without any prostheses. The combined relative standard uncertainty of dose measurement by electron spin resonance (ESR)/alanine was 5.05%, whereas the combined relative standard uncertainty of the applied dose was 3.35%, resulting in a combined relative standard uncertainty of the whole process of 6.06%. The ESR dosimetry indicated that there was no difference (P>0.05, ANOVA) in dosage between the planned dose and treatments. The results are in the range of the planned dose, within the combined relative uncertainty, demonstrating that the treatment-planning system compensates for the effects caused by the presence of femur and hip metal prostheses.

A dose-response curve for biodosimetry from a 6 MV electron linear accelerator

Biological dosimetry (biodosimetry) is based on the investigation of radiation-induced biological effects (biomarkers), mainly dicentric chromosomes, in order to correlate them with radiation dose. To interpret the dicentric score in terms of absorbed dose, a calibration curve is needed. Each curve should be constructed with respect to basic physical parameters, such as the type of ionizing radiation characterized by low or high linear energy transfer (LET) and dose rate. This study was designed to obtain dose calibration curves by scoring of dicentric chromosomes in peripheral blood lymphocytes irradiated in vitro with a 6 MV electron linear accelerator (Mevatron M, Siemens, USA). Two software programs, CABAS (Chromosomal Aberration Calculation Software) and Dose Estimate, were used to generate the curve. The two software programs are discussed; the results obtained were compared with each other and with other published low LET radiation curves. Both software programs resulted in identical linear and quadratic terms for the curve presented here, which was in good agreement with published curves for similar radiation quality and dose rates.

Ultrastructural changes of Fusobacterium nucleatum as a defense mechanism against human neutrophil peptide-1 - A Transmission Electron Microscopy (TEM) study

Aims: The aim of this work was to assess the ultrastructural changes, cellular proliferation, and the biofilm formation ability of F. nucleatum as defense mechanisms against the effect of HNP-1. Materials and methods: The type strain of F. nucleatum (ssp. nucleatum ATCC 25586) and two clinical strains (ssp. polymorphum AHN 9910 and ssp. nucleatum AHN 9508) were cultured and incubated with four different test concentrations of recombinant HNP-1 (1, 5, 10 and 20 µg/ml) and one control group (0 µg/ml). Bacterial pellets from each concentration were processed for TEM imaging. Planktonic growth was assessed and colony forming units (CFU) were measured to determine the cellular proliferation. Scrambled HNP-1 was used for confirmation. Results: TEM analyses revealed a decrease in the outer membrane surface corrugations and roughness of the strain AHN 9508 with increasing HNP-1 concentrations. In higher concentrations of HNP-1, the strain AHN 9910 showed thicker outer membranes with a number of associated rough vesicles attached to the outer surface. For ATCC 25586, the treated bacterial cells contained higher numbers of intracellular granules with increasing the peptide concentration. Planktonic growth of the two clinical strains were significantly enhanced (P<0.001) with gradually increased concentrations of HNP-1. None of the planktonic growth results of the 3 strains incubated with the scrambled HNP-1 was statistically significant. HNP-1 decreased the biofilm formation of the two clinical strains, AHN 9910 and 9508, significantly (P<0.01 and P<0.001; respectively). Conclusions: The present in vitro study demonstrates that F. nucleatum has the ability to withstand the lethal effects of HNP-1 even at concentrations simulating the diseased periodontium in vivo. The increase in planktonic growth could act as defense mechanisms of F. nucleatum against HNP-1.

Characterization of amine-based CO2 adsorbent for Direct Air Capture

Direct air capture technologies extract CO2 from air at a concentration of as low as 400ppm. The captured CO2 can be used for the production of synthetic methane or liquid fuels. In the literature survey of this thesis, results related to direct air capture by using solid sorbents are presented and critically discussed. In the experimental part, a proprietary amine functionalized resin is characterized for direct air capture. Structural comparison is also made to a commercial resin of similar type. Based on the literature survey, the most important parameters in direct air capture process are low adsorption and desorption temperatures, good cyclic stability in dry and humid conditions, high CO2 outlet purity and a high working capacity. Primary amine functionalized solid sorbents are found to often have good qualities for direct air capture, but overall process performance is rarely studied exhaustively. Based on FTIR spectra, both resin adsorbents are found to be consisted of polystyrene functionalized with primary amine, and capture CO2 by forming carbamate. The commercial resin is more porous, has a slightly higher particle size and contains fewer impurities. Important physical parameters are gained of the proprietary resin, such as internal porosity and median particle size. The resin’s amine group is found to endure thermal treatment reasonably well. CO2 adsorption capacity gained by thermal gravimetry from 400ppm CO2 is highest at 25oC, and is found to be reasonable compared to values presented in literature. Thus, the resin is stated to exhibit promising qualities for direct air capture.

Trends in fish prey capture by common terns following zebra mussel invasion : do terns track fish species abundance? /

The Common Tern (Sterna hirundo) is a ground nesting colonial seabird. Terns rely primarily on small prey fishes which they obtain through plunge diving for their survival as well as the survival of their offspring during the breeding season. The zebra mussel (Dreissena polymorpha) is a small bivalve mollusk that invaded North American waters in the late 1980's. Through its suspension feeding, the zebra mussel has the ability to alter the entire aquatic ecosystem, ultimately leading to a reduction in pelagic organisms including small prey fish. The objective of the study was to determine what (if any) indirect effects the invasion of the zebra mussel has had on fish prey captured by terns. The study took place in two separate two-year periods, 1990-91 and 1995-96 on a concrete breakwall off the north shore of Lake Erie near Port Colborne, Ontario. Daily nest checks revealed clutch initiation dates, egg-laying chronology, hatching success and morphological egg characteristics (length and breadth). Behavioural observations included time each sex spent in attendance with its brood, the frequency of feeding chicks and the prey species composition and size fed to chicks as well as to females (courtship feeding). Egg sizes did not differ between study periods, nor did feeding rates to chicks, suggesting that food was not a limiting resource. Terns spent less time with their broods (more time foraging) in the 1995-96 period. However, they also had significantly larger broods and fledged more offspring. The time of each individual foraging trip decreased, suggesting that fish were easier to obtain in 1995 and 1996. Lastly, kleptoparasitism rates decreased, suggesting that the costs of foraging (time, energy) actually decreased as fewer birds adopted this strategy to compensate for what I assumed to be a lack of available food (fish). The only significant difference between the periods of 1990, 1991 and 1995, 1996 was a change in diet. Terns delivered significantly fewer rainbow smelt and more emerald shiner in 1995 and 1996. However, the average size of fish delivered did not change. Thus, there was little impact on prey captured by Common Terns in Lake Erie since the invasion of the zebra mussel.

Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.

Comparison of two measures of PSI electron transport in winter rye

The number of P700 (the reaction centre of Photosystem I) converted to P700+, in winter rye, was determined by measuring the absorbance change at 820nm . It was found, with a single turnover flash, that thylakoids isolated from cold grown plants have a 50% greater number of P700 oxidized than thylakoids isolated from warm grown plants. Incubation of thylakoids in the dark at 35 C did not change the number of P700 oxidized. The conversion of P700 to P700+ with a single flash can be compared to a steady state rate of electron transport using a Clark electrode. The results for P700 oxidation using the absorbance change at 820 nm measure effects within the PSI complex whereas the results obtained from a Clark electrode measures steady state electron transport between the cytochrome blf complex and the PSI complex. In contrast to the results for P700 oxidation it was shown, using a Clark electrode, that both thylakoids from cold grown plants and thylakoids incubated at in the dark 35 C exhibited 50% higher rates of electron transport than thylakoids from warm grown plants. The correlation between the higher rate of steady state PSI electron transport observed in thylakoids isolated from cold grown winter rye and number of active PSI reaction centres localizes the site of the increase to the PSI reaction centre. In contrast the lack of correlation after incubation at 35 C indicates the increase in the rate of light saturated electron transport in thylakoids isolated from cold grown plants and thylakoids incubated in the dark at 35 C occur by different mechanisms.

Fast atom bombardment and electron impact mass spectrometry studies of some aryltin compounds and ferrocenes

Both El MS and FAB MS behavior of two groups of compounds, aryltin and ferrocene compounds, have been studied. For the aryltin compounds, the effect of substituent group position, substituent group type and ligand type on the El spectra have been explored in the El MS studies. The fragmentation mechanism has been investigated under El with linked scans, such as fragment ion scans(BJE), parent ion scans(B2JE) and constant neutral radical loss scans(B2(1-E)JE2). In the FAB MS studies, matrix optimization experiments have been carried out. The positive ion FAB MS studies focused on the effect of substituent group position, substituent group type and ligand type on the spectra. The fragmentation mechanisms of all the samples under positive ion FAB have been studied by means of the linked scans. The CA positive ion FAB fragmentation studies were also carried out for a typical sample. Negative ion FAB experiments of all the compounds have been done. And finally, the comparison of the El MS and FAB MS has been made. For ferrocenes, the studies concentrated on the fragmentation mechanism of each compound under El with linked scan techniques in the first field-free region and the applicability of positive/negative ion FAB MS to this group of compounds. The fragmentation mechanisms under positive ion FAB of those ferrocenes which can give positive ion FAB MS spectra were studied with the linked scan techniques. The CA +ve F AB fragmentation studies were carried out for a typical sample. Comparison of the E1 MS and FAB MS has been made.

Investigation of the composition of linear alkylbenzenes with emphasis on the identification and quantitation of some trace compounds using GS/MS system in both electron impact and chemical ionization modes

Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.

Light and electron microscope studies of host-parasite relations in a mycoparasite

Light microscope studies of the mycoparasite Piptocephalis virginiana revealed that the cylindrical spores of the parasite became spherical upon germination and produced 1-4 germ tubes. Generally t"l.vO germ tubes were produced by each spore. When this parasite was inoculated on its potential hosts, Choanephora cucurbitarum and Phascolomyces articulosus, the germ tube nearest to the host hypha continued to grow and made contact with the host hypha. The tip of the parasite's germ tube became swollen to form a distinct appressorium. Up to this stage the behavior of the parasite was similar regardless of the nature of the host. In the compatible host-parasite combination, the parasite penetrated the host, established a nutritional relationship and continued to grow to cover the host completely with its buff colored spores in 3-4 days. In the incompatible host-parasite combination, the parasite penetrated the host but its further advance was arrested. As a result of failure to establish a nutritional relationship with the resistant host, the parasite made further attempts to penetrate the host at different sites producing multiple infections. In the absence of nutrition the parasite weakened and the host outgrew the parasite completely. In the presence of a non-host species, Linderina pennispora the parasite continued to grow across the non-host 1).yp_hae vlithout establishing an initial contact. Germination studies showed that the parasite germinated equally well in the presence of host and non-host species. Further electron microscope studies revealed that the host-parasite interaction between P. virginiana and its host, C. cucurbi tarum, was compatible when the host hyphae were young slender, with a thin cell wall of one layer. The parasite appeared to penetrate mechanically by pushing the host-cell wall inward. The host plasma membrane invaginated along the involuted cell wall. The older hyphae of C. cucurbitarum possessed two distinct layers of cell wall and-showed an incompatible interaction when challenged vlith the parasite. At the point of contact, the outer layer of the host-cell wall dissolved, probably by enzymatic digestion, and the inner layer became thickened and developed a papilla as a result of its response to the parasite. The haustoria of the parasite in the old hyphae were always surrounded by a thick, well developed sheath, whereas the haustoria of the same age in the young host mycelium were devoid of a sheath during early stages of infection. Instead, they were in direct contact with the host protoplast. The incompatible interaction between a resistant host, P. articulosus and the parasite showed similar results as with the old hyphae of C. cucurbitarum. The cell wall of P. articulosus appeared thick-with two or more layers even in the 18-22 h-old hyphae. No contact or interaction was established between the parasite and the non-host L. pennispora. The role of cell wall in the resistance mechanism is discussed.

A time-resolved electron paramagnetic resonance spectroscopy study of paramagnetic porphyrins /

There is considerable interest in intramolecular energy transfer, especially in complexes which absorb visible light, because it is crucial to the better understanding of photoharvesting systems in photosynthetic organisms and for utilizing solar energy as well. Porphyrin dimers represent one of the best systems for the exploration of light-induced intramolecular energy transfer. Many kinds of porphyrins and porphyrin dimers have been studied over the past decade, however little attention has been paid to the influence of paramagnetic metals on the behavior of their excited states. In this thesis, Electron Paramagnetic Resonance Spectroscopy (EPR) is used to study such compounds. After light irradiation, porphyrins easily produce a variety of excited states, which are spin polarized and can be detected by the time-resolved (TR) EPR technique. The spin polarized results for vanadyl porphyrins, their electrostatically-coupled dimers, a covalently-linked copper porphyrin-free base porphyrin dimer, and free base porphyrins are presented in this thesis. From these results we can conclude that the spin polarization patterns of vanadyl porphyrins come primarily from the trip-quartet state generated by intersystem crossing (lSC) from the excited sing-doublet state through the trip-doublet state. The spin polarization pattern of electrostatically-coupled vanadyl porphyrin-free base porphyrin dimer is produced by the triplet state of the free base porphyrin half which is coupled to the unpaired electron on the vanadyl ion.

Letter from the Secretary of the Navy, transmitting the official account of the capture of the British sloop of War, Reindeer, by the United States sloop Wasp, commanded by Captain Johnston Blakeley, on the twenty-eighth June last.--

"A list of British vessels captured by the United States' sloop of War Wasp, J. Blakeley esg. commander, between May 1st and July 6th, 1814".Folded table at end.

Orientation of Non-Native 2-Monosubstituted and 2,3-Disubstituted 1,4-Naphthoquinones in the A1 binding site of PSI and the effect on the rate of electron transfer : an electron paramagnetic resonance spectroscopy study

The proce-ss ofoxygenic photosynthesis is vital to life on Earth. the central event in photosynthesis is light induced electron transfer that converts light into energy for growth. Ofparticular significance is the membrane bound multisubunit protein known as Photosystem I (PSI). PSI is a reaction centre that is responsible for the transfer of electrons across the membrane to reduce NADP+ to NADPH. The recent publication ofa high resolution X-ray structure of PSI has shown new information about the structure, in particular the electron transfer cofactors, which allows us to study it in more detail. In PSI, the secondary acceptor is crucial for forward electron transfer. In this thesis, the effect of removing the native acceptor phylloquinone and replacing it with a series of structurally related quinones was investigated via transient electron paramagnetic resonance (EPR) experiments. The orientation of non native quinones in the binding site and their ability to function in the electron transfer process was determined. It was found that PSI will readily accept alkyl naphthoquinones and anthraquinone. Q band EPR experiments revealed that the non-native quinones are incorporated into the binding site with the same orientation of the headgroup as in the native system. X band EPR spectra and deuteration experiments indicate that monosubstituted naphthoquinones are bound to the Al site with their side group in the position occupied by the methyl group in native PSI (meta to the hydrogen bonded carbonyl oxygen). X band EPR experiments show that 2, 3- disubstituted methyl naphthoquinones are also incorporated into the Al site in the same orientation as phylloquinone, even with the presence of a halogen- or sulfur-containing side chain in the position normally occupied by the phytyl tail ofphylloquinone. The exception to this is 2-bromo-3-methyl --.- _. -. - -- - - 4 _._ _ _ - _ _ naphthoquinone which has a poorly resolved spectrum, making determination of the orientation difficuh. All of the non-native quinones studied act as efficient electron acceptors. However, forward electron transfer past the quinone could only be demonstrated for anthraquinone, which has a more negative midpoint potential than phylloquinone. In the case of anthraquinone, an increased rate of forward electron transfer compared to native PSI was found. From these results we can conclude that the rate ofelectron transfer from Al to Fx in native PSI lies in the normal region ofthe Marcus Curve.