For x- and gamma- irradiations delivering entrance doses from 2- up to 1000 Gy to commercial 1.0 mm thick borosilicate glass microscope slides, study has been made of their thermoluminescence yield. With an effective atomic number of 10.6 (approximating bone equivalence), photon energy dependency is apparent in the low x-ray energy range, with interplay between the photoelectric effect and attenuation. As an example, over the examined dose range, at 120 kVp the photon sensitivity has been found to be some 5× that of 60Co gamma irradiations, also with repeatability to within ~1%. The glow-curves, taking the form of a single prominent broad peak, have been deconvolved yielding at best fit a total of five peaks, the associated activation energies and frequency factors also being obtained. The results indicate borosilicate glass slides to offer promising performance as a low-cost passive radiation dosimeter, with utility for both radiotherapy and industrial applications.
This study analysed thermoluminescence (TL) glow curves of the polymer pencil lead graphite (PPLG) due to its potential applications in radiation dosimetry. The TL glow curves provide information on the physical parameters of the defects participating in luminescence process. The glow curves for different diameters PPLG samples were obtained with varying temperature from 50 to 300 °C, at a fixed heating rate of 10 °Cs-1. A number of methods (initial rise, peak shape and curve fitting) were used to fit the TL glow peaks of the PPLG samples obtained under photon dose of 200 Gy. From the fitted TL signals, the trap parameters such as the order of kinetics, the activation energy, the frequency factor, etc. for the individual peaks were numerically determined. The lifetimes of TL process were calculated assuming the first-order kinetics. The results are compared among the different methods adopted in this study. Implications about the possible results in glow curve deconvolution are discussed.
Present work builds upon prior investigations concerning the novel use of graphite-rich polymer pencil-lead for passive radiation dosimetry. Working with photon-mediated interactions at levels of dose familiar in radiotherapy, exploratory investigations have now been made using graphite produced commercially in the form of 50 μm thick sheets. Focusing on the relationship between absorbed radiation energy and induced material changes, investigations have been made of thermo- and photoluminescence dose dependence, also of alterations in Raman spectroscopic features. Photoluminescence studies have focused on the degree of structural order of the samples when exposed to incident MeV energy gamma-radiation, supported by crystallite size evaluations. The results are consistent and evident of structural alterations, radiation-driven thermal annealing also being observed. The results, supportive of previous TL, Raman and photoluminescence studies, are readily understood to arise from irradiation changes occurring at the microscopic level. Notwithstanding the non-linearities observed in the conduct of Raman and photoluminescence studies there is clear potential for applications in use of the defect-dependent methods herein, providing sensitive detection of radiation damage in graphite and from it dose determination. Most specifically, the readily available thin graphite sheets can provide the basis of a low-cost yet highly effective system for studies of radiation-driven changes in carbon (and/or carbon based composites), also as a dosimetric probe of skin dose, its atomic number closely matching with the effective atomic number of soft tissues.
We explore the utility of controlled low-doses (0.2-100 Gy) of photon irradiation as initiators of structural alteration in carbon-rich materials. To-date our work on carbon has focused on β-, x- and γ-irradiations and the monitoring of radiotherapeutic doses (from a few Gy up to some tens of Gy) on the basis of the thermoluminescence (TL) signal, also via Raman and X-ray photo-spectroscopy (XPS), providing analysis of the dose dependence of single-walled carbon nanotubes (SWCNT). The work has been extended herein to investigate possibilities for analysis of structural alterations in graphite-rich mixtures, use being made of two grades of graphite-rich pencil lead, 8H and 2B, both being in the form produced for mechanical pencils (propelling or clutch pencils). 2B has the greater graphite content (approaching 98 wt %), 8H being a mixture of C, O, Al and Si (with respective weight percentages 39.2, 38.2, 9.8 and 12.8). Working on media pre-annealed at 400 °C, both have subsequently been irradiated to penetrating photon-mediated doses. Raman spectroscopy analysis has been carried out using a 532 nm laser Raman spectrometer, while for samples irradiated to doses from 1 to 40 Gy, XPS spectra were acquired using Al Kα sources (hv ∼1400 eV); carbon KLL Auger peaks were acquired using 50 eV Pass Energy. At these relatively low doses, alterations in order-disorder are clearly observed, defect generation and internal annealing competing as dominating effects across the dose range.
Preliminary study has been made of black human hair, carbon concentration of some 53%, a model in examining the potential of hair of the human head in retrospective and emergency biodosimetry applications, also offering effective atomic number near to that of water. The hair samples were exposed to [Formula: see text]Co gamma rays, delivering doses from 0 to 200 Gy. Structural alterations were observed, use being made of Raman and photoluminescence (PL) spectroscopy. Most prominent among the features observed in the first-order Raman spectra are the D and G peaks, appearing at 1370 [Formula: see text] and 1589 [Formula: see text] respectively, the intensity ratio [Formula: see text] indicating dose-dependent defects generation and annealing of structural alterations. The wavelengths of the PL absorption and emission peaks are found to be centred at [Formula: see text] nm and [Formula: see text] nm, respectively. The hair samples mean band gap energy ([Formula: see text]) post-irradiation was found to be [Formula: see text] eV, of the order of a semiconductor and approximately two times the [Formula: see text] of other carbon-rich materials reported via the same methodology.
The present study continues research into the utilisation of carbonaceous media for medical radiation dosimetry, focusing on the effects of surface area-to-volume ratio and carbon content on structural interaction alterations and dosimetric properties in sheet- and bead-type graphitic materials (with the respective carbon content of ∼98 wt% and ∼90 wt%). Using 60Co gamma-rays and doses from 0.5 Gy to 20 Gy, the study has been made of the response of commercially available graphite in the form of 0.1 mm, 0.2 mm, 0.3 mm and 0.5 mm thick sheets, also of activated carbon beads. Confocal Raman and photoluminescence spectroscopy have been employed, examining radiation-induced structural interaction alterations. Dose-dependent variation in the Raman intensity ratio ID/IG relates to the varying dominance of defect generation and dose-driven defect annealing. Of the various thickness graphite sheets, the 0.1 mm thick medium possesses the greatest surface area-to-volume ratio. Perhaps unsurprisingly, it also exhibits the greatest thermoluminescence (TL) yield compared to that of the other carbonaceous sheet foils used herein. Moreover, the second greatest mass-normalised TL yield has been observed to be that of the porous beads, reflected in the greater defect density (ID/IG > 2) when compared to the other media, due in part to their inherent feature of large internal surface area. Considering the challenge posed in matching skin thickness with skin dose, the near tissue equivalent graphite sheets show particular promise as a skin dosimeter, sensitive as a function of depth.
Epithelial-mesenchymal transition (EMT) is increasingly explored in cancer progression. Considering that triple negative (TN) breast cancer has the poorest survival among molecular subtypes, we investigated 49 TN, 45 luminal and 25 HER2-enriched female breast carcinomas for EMT expression (using E-cadherin and vimentin immunohistochemistry) against lymphovascular and/or lymph node invasion. E-cadherin and vimentin expressions were semi-quantitated for positive- cancer cells (0=0-<1%, 1=1-10%, 2 =11-50%, 3=>50%) and staining intensity (0=negative, 1=weak, 2=moderate, 3=strong), with final score (low=0-4 and high=6-9) derived by multiplying percentage and intensity scores for each marker. Low E-cadherin and/or high vimentin scores defined EMT positivity. Low E-cadherin co-existing with high vimentin defined "complete" (EMT-CV), while low E-cadherin (EMT-C) or high vimentin (EMT-V) occurring independently defined "partial" subsets. 38 (31.9%) cancers expressed EMT, while 59.2 % TN, 13.3% luminal and 12% HER2-enriched cancers expressed EMT (p<0.05). Among the cancers with lymphovascular and/or lymph node invasion, EMT positivity by molecular types were 66.7% TN, 7.4% luminal and 11.8% HER2-enriched (p<0.05). Although EMT-V, associated with stem-cell properties was the dominant TN EMT profile, EMT-CV, a profile linked to vascular metastases, was encountered only in TN. EMT appears important in TN cancer and different EMT profiles may be associated with its aggressive nature.
Over the past decade and more, considerable interest has been shown in the thermoluminescence (TL) properties of silica-based single-mode optical fibres, in particular investigating potential ionising radiation dosimetry applications. Herein, study has been made of TL glow curve, dose response, reproducibility and fading of 6mol% Ge-doped silica, fabricated in-house and produced in the form of cylindrical fibres. Three different pairings of doped-core and silica cladding diameters were produced: (40, 241)µm, (80, 483)µm and (100, 604)µm. The TL results were compared against that of TLD-100, one of the most sensitive commercially available LiF-based TL media. For all three pairings of diameters, closely similar TL glow curve were obtained, formed of a single peaked structure with a maximum TL yield located between the temperatures 250 and 310°C. The TL yield of the fibres were linear over the range of doses investigated, from 1Gy up to 10Gy, their dose response exceeding that of TLD-100, the samples also being found to be reusable, without evidence of degradation.
The sensitivity of a novel silica-based fibre-form thermoluminescence dosimeter was tested off-site of a rare-earths processing plant, investigating the potential for obtaining baseline measurements of naturally occurring radioactive materials. The dosimeter, a Ge-doped collapsed photonic crystal fibre (PCFc) co-doped with B, was calibrated against commercially available thermoluminescent dosimetry (TLD) (TLD-200 and TLD-100) using a bremsstrahlung (tube-based) x-ray source. Eight sampling sites within 1 to 20 km of the perimeter of the rare-earth facility were identified, the TLDs (silica- as well as TLD-200 and TLD-100) in each case being buried within the soil at fixed depth, allowing measurements to be obtained, in this case for protracted periods of exposure of between two to eight months. The values of the dose were then compared against values projected on the basis of radioactivity measurements of the associated soils, obtained via high-purity germanium gamma-ray spectrometry. Accord was found in relative terms between the TL evaluations at each site and the associated spectroscopic results. Thus said, in absolute terms, the TL evaluated doses were typically less than those derived from gamma-ray spectroscopy, by ∼50% in the case of PCFc-Ge. Gamma spectrometry analysis typically provided an upper limit to the projected dose, and the Marinelli beaker contents were formed from sieving to provide a homogenous well-packed medium. However, with the radioactivity per unit mass typically greater for smaller particles, with preferential adsorption on the surface and the surface area per unit volume increasing with decrease in radius, this made for an elevated dose estimate. Prevailing concentrations of key naturally occurring radionuclides in soil,226Ra,232Th and40K, were also determined, together with radiological dose evaluation. To date, the area under investigation, although including a rare-earth processing facility, gives no cause for concern from radiological impact. The current study reveals the suitability of the optical fibre based micro-dosimeter for all-weather monitoring of low-level environmental radioactivity.
We provide retrospective analysis of a consolidated set of confocal Raman microspectrometry and photoluminescence data for irradiated graphitic materials, detecting the generation of low-dose defects. Within the dose range 0.1 Gy-0.2 kGy, one attracting marginal attention in previous radiation damage studies, an effect is seen that potentially seeds material weakening, the pooled data covering independent x-, gamma-rays, and thermal neutron field irradiations. Categorised in terms of a number of key influencing factors, an emergent pattern of response for the various samples under study is observed, indicative of the cycling of radiation driven energy storage and subsequent relaxation. This novel technique, to be referred to herein as defectroscopy, provides a probe of the generation of radiation-induced defects and internal annealing, the strength of the effects being strongly identified to arise from a combination of the ratio of surface area to volume of the samples, fractional carbon content, linear energy transfer, and strain-related defects within the initial material. These examinations offer a first step in considering whether the technique offers wider applicability, not least in early determination of changes in materials with widespread importance in structural and functional roles.
Bladder cancer is the fourth most common malignancy in males. It can present across the whole continuum of severity, from mild through well-differentiated disease to extremely malignant tumours with poor survival rates. As with other vital organ malignancies, proper clinical management involves accurate diagnosis and staging. Chemotherapy consisting of a cisplatin-based regimen is the mainstay in the management of muscle-invasive bladder cancers. Control via cisplatin-based chemotherapy is threatened by the development of chemoresistance. Intracellular cholesterol biosynthesis in bladder cancer cells is considered a contributory factor in determining the chemotherapy response. Farnesyl-diphosphate farnesyltransferase 1 (FDFT1), one of the main regulatory components in cholesterol biosynthesis, may play a role in determining sensitivity towards chemotherapy compounds in bladder cancer. FDFT1-associated molecular identification might serve as an alternative or appendage strategy for early prediction of potentially chemoresistant muscle-invasive bladder cancer tissues. This can be accomplished using Raman spectroscopy. Developments in the instrumentation have led to it becoming one of the most convenient forms of analysis, and there is a highly realistic chance that it will become an effective tool in the pathology lab. Chemosensitive bladder cancer tissues tend to have a higher lipid content, more protein genes and more cholesterol metabolites. These are believed to be associated with resistance towards bladder cancer chemotherapy. Herein, Raman peak assignments have been tabulated as an aid to indicating metabolic changes in bladder cancer tissues that are potentially correlated with FDFT1 expression.
At the supramolecular level, the proliferation of invasive ductal carcinoma through breast tissue is beyond the range of standard histopathology identification. Using synchrotron small angle x-ray scattering (SAXS) techniques, determining nanometer scale structural changes in breast tissue has been demonstrated to allow discrimination between different tissue types. From a total of 22 patients undergoing symptomatic investigations, different category breast tissue samples were obtained in use of surgically removed tissue, including non-lesional, benign and malignant tumour. Structural components of the tissues were examined at momentum transfer values between q = 0.2 nm-1 and 1.5 nm-1. From the SAXS patterns, axial d-spacing and diffuse scattering intensity were observed to provide the greatest discrimination between the various tissue types, specifically in regard to the epithelial mesenchymal transition (EMT) structural component in malignant tissue. In non-lesional tissue the axial period of collagen is within the range 63.6-63.7 nm (formalin fixed paraffin embedded (FFPE) dewaxed) and 63.4 (formalin fixed), being 0.9 nm smaller than in EMT cancer-invaded regions. The overall intensity of scattering from cancerous regions is a degree of magnitude greater in cancer-invaded regions. Present work has found that the d-spacing of the EMT positive breast cancer tissue (FFPE (dewaxed)) is within the range 64.5-64.7 nm corresponding to the 9th and 10th order peaks. Of particular note in regard to formalin fixation of samples is that no alteration is observed to occur in the relative differences in collagen d-spacing between non-lesional and malignant tissues. This is a matter of great importance given that preserved-sample and also retrospective study of samples is greatly facilitated by formalin fixation. Present results indicate that as aids in tissue diagnosis SAXS is capable of distinguishing areas of invasion by disease as well as delivering further information at the supramolecular level.
Amyloidosis is a deleterious condition caused by abnormal amyloid fibril build-up in living tissues. To date, 42 proteins that are linked to amyloid fibrils have been discovered. Amyloid fibril structure variation can affect the severity, progression rate, or clinical symptoms of amyloidosis. Since amyloid fibril build-up is the primary pathological basis for various neurodegenerative illnesses, characterization of these deadly proteins, particularly utilising optical techniques have been a focus. Spectroscopy techniques provide significant non-invasive platforms for the investigation of the structure and conformation of amyloid fibrils, offering a wide spectrum of analyses ranging from nanometric to micrometric size scales. Even though this area of study has been intensively explored, there still remain aspects of amyloid fibrillization that are not fully known, a matter hindering progress in treating and curing amyloidosis. This review aims to provide recent updates and comprehensive information on optical techniques for metabolic and proteomic characterization of β-pleated amyloid fibrils found in human tissue with thorough literature analysis of publications. Raman spectroscopy and SAXS are well established experimental methods for study of structural properties of biomaterials. With suitable models, they offer extended information for valid proteomic analysis under physiologically relevant conditions. This review points to evidence that despite limitations, these techniques are able to provide for the necessary output and proteomics indication in order to extrapolate the aetiology of amyloid fibrils for reliable diagnostic purposes. Our metabolic database may also contribute to elucidating the nature and function of the amyloid proteome in development and clearance of amyloid diseases.
Trace and minor elements play crucial roles in a variety of biological processes, including amyloid fibrils formation. Mechanisms include activation or inhibition of enzymatic reactions, competition between elements and metal proteins for binding positions, also changes to the permeability of cellular membranes. These may influence carcinogenic processes, with trace and minor element concentrations in normal and amyloid tissues potentially aiding in cancer diagnosis and etiology. With the analytical capability of the spectroscopic technique X-ray fluorescence (XRF), this can be used to detect and quantify the presence of elements in amyloid characterization, two of the trace elements known to be associated with amyloid fibrils. In present work, involving samples from a total of 22 subjects, samples of normal and amyloid-containing tissues of heart, kidney, thyroid, and other tissue organs were obtained, analyzed via energy-dispersive X-ray fluorescence (EDXRF). The elemental distribution of potassium (K), calcium (Ca), arsenic (As), and iron (Fe) was examined in both normal and amyloidogenic tissues using perpetual thin slices. In amyloidogenic tissues the levels of K, Ca, and Fe were found to be less than in corresponding normal tissues. Moreover, the presence of As was only observed in amyloidogenic samples; in a few cases in which there was an absence of As, amyloid samples were found to contain Fe. Analysis of arsenic in amyloid plaques has previously been difficult, often producing contradictory results. Using the present EDXRF facility we could distinguish between amyloidogenic and normal samples, with potential correlations in respect of the presence or concentration of specific elements.
Study has been made of the thermoluminescence yield of various novel tailor-made silica fibres, 6 and 8 mol % Ge-doped, with four differing outer dimensions, comprised of flat and cylindrical shapes, subjected to electron irradiation. Main thermoluminescence dosimetric characteristics have been investigated, including the glow curve, dose response, energy dependence, minimum detectable dose, effective atomic number, linearity of index and sensitivity of the fibres. The studies have also established the uncertainties involved as well as the stability of response in terms of fading effect, reproducibility and annealing. In addition, dose-rate dependence was accounted for as this has the potential to be a significant factor in radiotherapy applications. The 6 and 8 mol % fibres have been found to provide highly linear dose response within the range 1 to 4 Gy, the smallest size flat fibre, 6 mol% Ge-doped, showing the greatest response by a factor of 1.1 with respect to the highly popular LiF phosphor-based medium TLD100. All of the fibres also showed excellent reproducibility with a standard deviation of < 2% and < 4% for 6 and 8 mol % Ge-doped fibres respectively. For fading evaluation, the smallest 6 mol% Ge-doped dimension flat fibre, i.e., 85 × 270 μm displayed the lowest signal loss within 120 days post-irradiation, at around 26.9% also showing a response superior to that of all of the other fibres. Moreover, all the fibres and TLD-100 chips showed independence with respect to electron irradiation energy and dose-rate. Compared with the 8 mol% Ge-doped optical fibres, the 6 mol% Ge-doped flat optical fibres have been demonstrated to possess more desirable performance features for passive dosimetry, serving as a suitable alternative to TLD-100 for medical irradiation treatment applications.
Using irradiated doped-silica preforms from which fibres for thermoluminescence dosimetry applications can be fabricated we have carried out a range of luminescence studies, the TL yield of the fibre systems offering many advantages over conventional passive dosimetry types. In this paper we investigate such media, showing emission spectra for irradiated preforms and the TL response of glass beads following irradiation to an 241Am-Be neutron source located in a tank of water, the glass fibres and beads offering the advantage of being able to be placed directly into liquid. The outcomes from these and other lines of research are intended to inform development of doped silica radiation dosimeters of versatile utility, extending from environmental evaluations through to clinical and industrial applications.
Accidents resulting in widespread dispersal of radioactive materials have given rise to a need for materials that are convenient in allowing individual dose assessment. The present study examines natural Dead Sea salt adopted as a model thermoluminescence dosimetry system. Samples were prepared in two different forms, loose-raw and loose-ground, subsequently exposed to 60Co gamma-rays, delivering doses in the range 2-10 Gy. Key thermoluminescence (TL) properties were examined, including glow curves, dose response, sensitivity, reproducibility and fading. Glow curves shapes were found to be independent of given dose, prominent TL peaks for the raw and ground samples appearing in the temperature ranges 361-385 ºC and 366-401 ºC, respectively. The deconvolution of glow curves has been undertaken using GlowFit, resulting in ten overlapping first-order kinetic glow peaks. For both sample forms, the integrated TL yield displays linearity of response with dose, the loose-raw salt showing some 2.5 × the sensitivity of the ground salt. The samples showed similar degrees of fading, with respective residual signals 28 days post-irradiation of 66% and 62% for the ground and raw forms respectively; conversely, confronted by light-induced fading the respective signal losses were 62% and 80%. The effective atomic number of the Dead Sea salt of 16.3 is comparable to that of TLD-200 (Zeff 16.3), suitable as an environmental radiation monitor in accident situations but requiring careful calibration in the reconstruction of soft tissue dose (soft tissue Zeff 7.2). Sample luminescence studies were carried out via Raman and Photoluminescence spectroscopy as well as X-ray diffraction, ionizing radiation dependent variation in lattice structure being found to influence TL response.