A luminescent edge-interlocked heteroleptic metallocage based on Cu3(pyrazolate)3 was prepared through a ligand replacement reaction from a homoleptic metallocage and a new ligand. Its structure was confirmed by XRD and MALDI-TOF mass spectrometry. Theoretical calculations revealed the new ligand was evidently responsible for the bathochromic shift of the optimal excitation. This work provides a heteroleptic strategy to regulate the interlocking fashion and photophysical mechanism of metallocages based on Cu3(pyrazolate)3.
Study has been undertaken of the thermoluminescence (TL) yield of various tailor-made flat cross-section 6 mol% Ge-doped silica fibers, differing only in respect of external dimensions. Key TL dosimetric characteristics have been investigated, including glow curves, dose response, sensitivity, fading and reproducibility. Using a (60)Co source, the samples were irradiated to doses within the range 1 to 10 Gy. Prior to irradiation, the flat fibers were sectioned into 6 mm lengths, weighed, and annealed at 400 °C for 1 h. TL readout was by means of a Harshaw Model 3500 TLD reader, with TLD-100 chips (LiF:Mg, Ti) used as a reference dosimeter to allow the relative response of the fibers to be evaluated. The fibers have been found to provide highly linear dose response and excellent reproducibility over the range of doses investigated, demonstrating high potential as TL-mode detectors in radiation medicine applications. Mass for mass, the results show the greatest TL yield to be provided by fibers of the smallest cross-section, analysis indicating this to be due to minimal light loss in transport of the TL through the bulk of the silica medium.
This study was carried out to investigate the suitability of using the optically stimulated luminescence dosimeter (OSLD) in measuring surface dose during radiotherapy. The water equivalent depth (WED) of the OSLD was first determined by comparing the surface dose measured using the OSLD with the percentage depth dose at the buildup region measured using a Markus ionization chamber. Surface doses were measured on a solid water phantom using the OSLD and compared against the Markus ionization chamber and Gafchromic EBT3 film measurements. The effect of incident beam angles on surface dose was also studied. The OSLD was subsequently used to measure surface dose during tangential breast radiotherapy treatments in a phantom study and in the clinical measurement of 10 patients. Surface dose to the treated breast or chest wall, and on the contralateral breast were measured. The WED of the OSLD was found to be at 0.4 mm. For surface dose measurement on a solid water phantom, the Markus ionization chamber measured 15.95% for 6 MV photon beam and 12.64% for 10 MV photon beam followed by EBT3 film (23.79% and 17.14%) and OSLD (37.77% and 25.38%). Surface dose increased with the increase of the incident beam angle. For phantom and patient breast surface dose measurement, the response of the OSLD was higher than EBT3 film. The in-vivo measurements were also compared with the treatment planning system predicted dose. The OSLD measured higher dose values compared to dose at the surface (Hp(0.0)) by a factor of 2.37 for 6 MV and 2.01 for 10 MV photon beams, respectively. The measurement of absorbed dose at the skin depth of 0.4 mm by the OSLD can still be a useful tool to assess radiation effects on the skin dermis layer. This knowledge can be used to prevent and manage potential acute skin reaction and late skin toxicity from radiotherapy treatments.
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.
Seven species of Mycena are reported as luminescent, representing specimens collected in Belize, Brazil, Dominican Republic, Jamaica, Japan (Bonin Islands), Malaysia (Borneo) and Puerto Rico. Four of them represent new species (Mycena luxaeterna, M. luxarboricola, M. luxperpetua, M. silvaelucens) and three represent new reports of luminescence in previously described species (M. aff. abieticola, M. aspratilis, M. margarita). Mycena subepipterygia is synonymized with M. margarita, and M. chlorinosma is proposed as a possible synonym. Comprehensive descriptions, illustrations, photographs and comparisons with phenetically similar species are provided. A redescription of M. chlorophos, based on analyses of type specimens and recently collected topotypical material, is provided. The addition of these seven new or newly reported luminescent species of Mycena brings the total to 71 known bioluminescent species of fungi.
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.
: In this work the influence of carbon nano-dots (CNDs) on absorption of ultra violet (UV) spectra in hybrid PVA based composites was studied. The FTIR results reveal the complex formation between PVA and CNDs. The shifting was observed in XRD spectrum of PVA:CNDs composites compared to pure PVA. The Debye-Scherrer formula was used to calculate the crystallite size of CNDs and crystalline phases of pure PVA and PVA:CNDs composites. The FESEM images emphasized the presence and dispersion of C-dots on the surface of the composite samples. From the images, a strong and clear absorption was noticed in the spectra. The strong absorption that appeared peaks at 280 nm and 430 nm can be ascribed to the n-π* and π-π* transitions, respectively. The absorption edge shifted to lower photon energy sides with increasing CNDs. The luminescence behavior of PVA:CNDs composite was confirmed using digital and photo luminescence (PL) measurements. The optical dielectric constant which is related to the density of states was studied and the optical band gap was characterized accurately using optical dielectric loss parameter. The Taucs model was used to determine the type of electronic transition in the samples.
Five luminescent polymorphic aggregates of trinuclear Cu(i)-pyrazolate, namely [anti-Cu3L3]2 (1), [syn-Cu3L3·C2H5OH]2 (2), [anti-Cu3L3·C2H5OH]n (3), [anti-Cu3L3·0.5C7H8]n (4) and [syn-Cu3L3·C8H10]n (5) (HL = 4-(pyridin-4-ylthio)-3,5-dimethyl-1H-pyrazole), were reported. The trimeric Cu3L3 fragments present syn- and anti-conformations dependent on the dangled direction of 4-pyridyl groups on the two sides of the Cu3Pz3 plane (Pz = pyrazolate). Intertrimeric NPyCu weak coordination bonds associate these Cu3L3 fragments together to form dimeric or polymeric structures, which are further stabilized by crystallized solvent molecules or intertrimeric CuCu interactions. The solvated complexes (3-5) may be transformed into the unsolvated complex 1 by evacuation of the crystallized solvents upon heating. All these complexes emit from green to yellow under UV irradiation, which originated from the triplet excited states of metal to ligand charge transfer (3MLCT) mixed with intertrimeric CuCu interactions. This work provides a novel kind of supramolecular aggregate based on Cu3Pz3 beyond the classical π-acidbase adducts and metallophilicity-dependent dimers/oligomers.
The assessment of surface dose is essential in radiotherapy to avoid deterministic effect or to
reduce the severity of side effects from radiation treatment. In this study, the surface dose for breast
cancer radiotherapy was measured using two types of dosimeter; Thermoluminescent Dosimeter
(TLD) and Optically Stimulated Luminescent Dosimeter (OSLD). The study was performed on the
left breast of female Alderson Radiation Therapy (ART) phantom. The treatment planning was
carried out on the ART phantom to determine the homogeneity of dose distribution within the target
organ is complied with the tolerance limits of 95% to 107% as recommended by the International
Commission on Radiation Units and Measurements (ICRU)’s Report No. 50. From the treatment
planning result, the phantom then was irradiated with 267 cGy dose per fraction for two beam
fields; medial tangential and lateral tangential fields using a 6 MV photon beam produced from
three-dimensional (3D) conformal radiotherapy. Result shows that the OSLD provides 25.7% and
23.5% higher surface dose compared to TLD for medial tangential and lateral tangential fields,
respectively. This condition may be due to higher effective point of measurement and angular
dependence of the OSLD compared to TLD. As a conclusion, suitable dosimeter should be selected
to ensure accurate estimation of surface dose could be made thus reduction of skin reaction to
patient could be achieved.
The exposure of food to ionizing radiation is being progressively used in many countries to
inactivate food pathogens, to eradicate pests and to extend shelf-life of food. To ensure free
consumer choice, irradiated food will be labeled. The availability of a reliable method to detect
irradiated food is important to enforce legal controls on labeling requirements, ensure proper
distribution and increase consumer confidence. This paper reports on the preliminary application
of photostimulated luminescence technique (PSL) as a potential method to detect irradiated food
and perhaps be used for monitoring irradiated food on sale locally in the near future. Thus this
study will be beneficial and relevant for application of food irradiation towards improving food
safety and security in Malaysia.
Human activities in a large array of industrial and agricultural sectors produce chemical contaminants which are chiefly hydrocarbons of various types that are potentially toxic and carcinogenic to aquatic and terrestrial organisms. Globally, millions of tons of these pollutants are generated annually, and in some areas, they are released indiscriminately to the environment. In order to overcome this problem, microbiological decontamination or bioremediation has been suggested. Bioremediation has been argued to be an efficient, economic, and adaptable alternative to physicochemical remediation. However, to date, such claims of successful bioremediation are often not supported by evidence from toxicity studies. In this regard, luminescent bacteria have been employed in some hydrocarbon remediation experiments to denote reduction in toxicity. In this review, the utilization of luminescence bacteria as toxicity monitoring agent for hydrocarbon remediation is discussed.
Study of a series of lead lithium borophosphate glass samples was performed to determine the structural and luminescence properties. The glass samples containing the composition of 20Pb0-xLi20-30B 20 3-(50-x)P 20 5-2TiO 2 (where x = 0, 5, 10, 15, 20) system were prepared using melt-quenching technique. The Pb0-Li20-B 20 3-P20 5-Ti0 2 samples were investigated for structural properties using Fourier transform infrared and photoluminescence spectroscopy for studies of luminescence properties. The results from FTIR showed the presence of trigonal and tetrahedral PO4' PO3, BO4 and B03 groups within the host network structure. The samples exhibit luminescence emission centered at 420, 482 and 496 nm when excited at 300 nm wavelength. The emission peak at 420 nm were assigned to F center emission and charge-transfer transition of Ti4+ ions. The results showed that emission intensity was dependent on lithium contents in Ti-doped lead lithium borophosphate glass composition.
This study characterises and evaluates an Al2O3:C-based optically stimulated luminescent dosemeter (OSLD) system, commercially known as the nanoDot™ dosemeter and the InLight® microStar reader, for personal and in vivo dose measurements in diagnostic radiology. The system characteristics, such as dose linearity, reader accuracy, reproducibility, batch homogeneity, energy dependence and signal stability, were explored. The suitability of the nanoDot™ dosemeters was evaluated by measuring the depth dose curve, in vivo dose measurement and image perturbation. The nanoDot™ dosemeters were observed to produce a linear dose with ±2.8% coefficient variation. Significant batch inhomogeneity (8.3%) was observed. A slight energy dependence (±6.1%) was observed between 60 and 140 kVp. The InLight® microStar reader demonstrated good accuracy and a reproducibility of ±2%. The depth dose curve measured using nanoDot™ dosemeters showed slightly lower responses than Monte Carlo simulation results. The total uncertainty for a single dose measurement using this system was 11%, but it could be reduced to 9.2% when energy dependence correction was applied.
Quorum sensing regulates bacterial virulence determinants, therefore making it an interesting target to attenuate pathogens. In this work, we screened edible, endemic plants in Malaysia for anti-quorum sensing properties. Extracts from Melicope lunu-ankenda (Gaertn.) T. G. Hartley, a Malay garden salad, inhibited response of Chromobacterium violaceum CV026 to N-hexanoylhomoserine lactone, thus interfering with violacein production; reduced bioluminescence expression of E. coli [pSB401], disrupted pyocyanin synthesis, swarming motility and expression of lecA::lux of Pseudomonas aeruginosa PAO1. Although the chemical nature of the anti-QS compounds from M. lunu-ankenda is currently unknown, this study proves that endemic Malaysian plants could serve as leads in the search for anti-quorum sensing compounds.
With interest in the potential of optical fibres as the basis of next-generation thermoluminescence dosimeters (TLDs), the development of suitable forms of material and their fabrication has become a fast-growing endeavour. Present study focuses on three types of Ge-doped optical fibres with different structural arrangements and/or shapes, namely conventional cylindrical fibre, capillary fibre, and flat fibre, all fabricated using the same optical fibre preform. For doses from 0.5 to 8 Gy, obtained at electron and photon energies, standard thermoluminescence (TL) characteristics of the optical fibres have been the subject of detailed investigation. The results show that in collapsing the capillary fibre into a flat shape, the TL yield is increased by a factor of 5.5, the yield being also some 3.2 times greater than that of the conventional cylindrical fibre fabricated from the same perform. This suggests a means of production of suitably sensitive TLD for in-vivo dosimeter applications. Addressing the associated defects generating luminescence from each of the optical fibres, the study encompasses analysis of the TL glow curves, with computerized glow curve deconvolution (CGCD) and 2(nd) order kinetics.
We report emerging circularly polarized luminescence (CPL) at 4f-4f transitions when lanthanide (EuIII and TbIII) tris(β-diketonate) embedded to cellulose triacetate (CTA), cellulose acetate butyrate (CABu), D-/L-glucose pentamethyl esters ( D-/ L-Glu), and D-/L-arabinose tetramethyl esters ( D-/ L-Ara) are in film states. Herein, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (fod) and 2,2,6,6-tetramethyl-3,5-heptanedione (dpm) were chosen as the β-diketonates. The glum value of Eu(fod)3 in CABu are +0.0671 at 593 nm (5
D
0
→
7
F1) and -0.0059 at 613 nm (5
D
0
→
7
F2), respectively, while those in CTA are +0.0463 and -0.0040 at these transitions, respectively. The glum value of Tb(fod)3 in CABu are -0.0029 at 490 nm (5
D
4
→
7
F6), +0.0078 at 540 nm (5
D
4
→
7
F5), and -0.0018 at 552 nm (5
D
4
→
7
F5), respectively, while those in CTA are -0.0053, +0.0037, and -0.0059 at these transitions, respectively. D-/ L-Glu and D-/ L-Ara induced weaker glum values at 4f-4f transitions of Eu(fod)3, Tb(fod)3, and Tb(dpm)3. For comparison, Tb(dpm)3 in α-pinene showed clear CPL characteristics, though Eu(dpm)3 did not. A surplus charge neutralization hypothesis was applied to the origin of attractive intermolecular interactions between the ligands and saccharides. This idea was supported from the concomitant opposite tendency in upfield 19F-NMR and downfield 1H-NMR chemical shifts of Eu(fod)3 and the opposite Mulliken charges between F-C bonds (fod) and H-C bonds (CTA and D-/ L-Glu). An analysis of CPL excitation (CPLE) and CPL spectra suggests that (+)- and (-)-sign CPL signals of EuIII and TbIII at different 4f-4f transitions in the visible region are the same with the (+)-and (-)-sign exhibited by CPLE bands at high energy levels of EuIII and TbIII in the near-UV region.
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.
DNAzymes have emerged as an important class of sensors for a wide variety of metal ions, with florescence DNAzyme sensors as the most widely used in different sensing and imaging applications because of their fast response time, high signal intensity, and high sensitivity. However, the requirements of an external excitation light source and its associated power increase the cost and size of the fluorometer, making it difficult to be used for portable detections. To overcome these limitations, we report herein a DNAzyme sensor that relies on chemiluminescence resonance energy transfer (CRET) without the need for external light. The sensor is constructed by combining the functional motifs from both Pb2+-dependent 8-17 DNAzyme conjugated to fluorescein (FAM) and hemin/G-quadruplex that mimics horseradish peroxidase to catalyze the oxidation of luminol by H2O2 to yield chemiluminescence. In the absence of Pb2+, the hybridization between the enzyme and substrate strands bring the FAM and hemin/G-quadruplex in close proximity, resulting in CRET. The presence of Pb2+ ions can drive the cleavage on the substrate strand, resulting in a sharp decrease in the melting temperature of hybridization and thus separation of the FAM from hemin/G-quadruplex. The liberated CRET pair causes a ratiometric increase in the donor's fluorescent signal and a decrease in the acceptor signal. Using this method, Pb2+ ions have been measured rapidly (<15 min) with a low limit of detection at 5 nM. By removing the requirement of exogenous light excitation, we have demonstrated a simple and portable detection using a smartphone, making the DNAzyme-CRET system suitable for field tests of lake water. Since DNAzymes selective for other metal ions or targets, such as bacteria, can be obtained using in vitro selection, the method reported here opens a new avenue for rapid, portable, and ratiometric detection of many targets in environmental monitoring, food safety, and medical diagnostics.
Chemiluminescence assay was used to assess the respiratory burst activities of polymorpho-nuclear leukocytes from paediatric patients reported to manifest with several episodes of recurrent bacterial infections. From this group of patients evaluated, only 10 cases of severe recurrent bacterial abscess exhibited more than 80% depression in the phagocytic chemilumi-nescence responses. The assay, being a sensitive method, was able to provide further useful laboratory investigation in diagnosing 4 patients with chronic granulomatous disease.