Investigation has been made of the radioluminescence dose response of Ge-doped silica flat and cylindrical fibers subjected to 6 and 10 MV photon beams. The fibers have been custom fabricated, obtaining Ge dopant concentrations of 6 and 10 mol%, subsequently cut into 20 mm lengths. Each sample has been exposed under a set of similar conditions, with use made of a fixed field size and source to surface distance (SSD). Investigation of dosimetric performance has involved radioluminescence linearity, dose-rate dependence, energy dependence, and reproducibility. Mass for mass, the 6 mol% Ge-doped samples provided the greater radioluminescence yield, with both flat and cylindrical fibers responding linearly to the absorbed dose. Further found has been that the cylindrical fibers provided a yield some 38% greater than that of the flat fibers. At 6 MV, the cylindrical fibers were also found to exhibit repeatability variation of <1%, superior to that of the flat fibers, offering strong potential for use in real-time dosimetry applications.
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.
Real-time and visual monitoring of pollutants in the air is of great importance since they are usually cannot be seen, smelled, or touched. Lanthanide nano-cluster is a kind of luminescent sensor for various species. However, controlling synthesis of lanthanide nano-cluster remains experimentally challenging. In this work, four series of lanthanide-barium (Ln-Ba) nano-clusters of Dy2Ba (1), Tb2Ba2 (2), Ln4Ba3 (Ln = Tb, 3a; Eu, 3b), Tb4Ba4 (4) were assembled through precisely controlling the pH of the reactant solutions. The work features the first example that the number of cluster's nuclei changes regularly with the pH. Moreover, investigation reveals that nano-cluster 3a is a highly selective and sensitive sensor towards acetylacetone (acac) and aniline. Interestingly, easy-to-use sensing devices of test paper, agarose gel, and five kinds of film on CaCO3, polyfoam, coin, mask, and wall that based on 3a were fabricated by facile methods. The seven sensing devices showed remarkable ability to sense aniline and acac vapors with visibility to the naked eyes. This is the first work on multiple real-time and visual sensing devices based on the lanthanide nano-cluster.
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.
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.
In recent years, the field of nanophotonics has progressively developed. However, constant demand for the development of new light source still exists at the nanometric scale. Light emissions from graphene-based active materials can provide a leading platform for the development of two dimensional (2-D), flexible, thin, and robust light-emitting sources. The exceptional structure of Dirac's electrons in graphene, massless fermions, and the linear dispersion relationship with ultra-wideband plasmon and tunable surface polarities allows numerous applications in optoelectronics and plasmonics. In this article, we present a comprehensive review of recent developments in graphene-based light-emitting devices. Light emissions from graphene-based devices have been evaluated with different aspects, such as thermal emission, electroluminescence, and plasmons assisted emission. Theoretical investigations, along with experimental demonstration in the development of graphene-based light-emitting devices, have also been reviewed and discussed. Moreover, the graphene-based light-emitting devices are also addressed from the perspective of future applications, such as optical modulators, optical interconnects, and optical sensing. Finally, this review provides a comprehensive discussion on current technological issues and challenges related to the potential applications of emerging graphene-based light-emitting devices.
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.
Present work concerns polymer pencil-lead graphite (PPLG) and the potential use of these in elucidating irradiation-driven structural alterations. The study provides detailed analysis of radiation-induced structural interaction changes and the associated luminescence that originates from the energy absorption. Thermally stimulated emission from the different occupied defect energy levels reflects the received radiation dose, different for the different diameter PPLGs. The PPLG samples have been exposed to photon irradiation, specifically x-ray doses ranging from 1 to 10 Gy, extended to 30-200 Gy through use of a60Co gamma-ray source. Trapping parameters such as order of kinetics, activation energy and frequency factor are estimated using Chen's peak-shape method for a fixed-dose of 30 Gy. X-ray diffractometry was used to characterize the crystal structure of the PPLG, the aim being to identify the degree of structural order, atomic spacing and lattice constants of the various irradiated PPLG samples. The mean atomic spacing and degree of structural order for the different diameter PPLG are found to be 0.3332 nm and 26.6° respectively. Photoluminescence spectra from PPLG arising from diode laser excitation at 532 nm consist of two adjacent peaks, 602 nm (absorption) and 1074 nm (emission), with mean energy band gap values within the range 1.113-1.133 eV.
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.
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.
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.
G-quadruplexes are made up of guanine-rich RNA and DNA sequences capable of forming noncanonical nucleic acid secondary structures. The base-specific sterical configuration of G-quadruplexes allows the stacked G-tetrads to bind certain planar molecules like hemin (iron (III)-protoporphyrin IX) to regulate enzymatic-like functions such as peroxidase-mimicking activity, hence the use of the term DNAzyme/RNAzyme. This ability has been widely touted as a suitable substitute to conventional enzymatic reporter systems in diagnostics. This review will provide a brief overview of the G-quadruplex architecture as well as the many forms of reporter systems ranging from absorbance to luminescence readouts in various platforms. Furthermore, some challenges and improvements that have been introduced to improve the application of G-quadruplex in diagnostics will be highlighted. As the field of diagnostics has evolved to apply different detection systems, the need for alternative reporter systems such as G-quadruplexes is also paramount.
Enhanced red and orange fluorescence emissions of Sm3+ Rare earth (RE) ions were observed in sodium‑zinc tellurite glasses embedded with silver and gold nanoparticles (NPs). The fine distribution of NPs in the glass matrix with an average diameter ~ 11.09 nm and ~3.86 nm for Ag and Au NPs respectively were confirmed by using transmission electron microscope (TEM). The embedding of Ag and Au NPs into the glass structure caused an increasing in the transition emission intensity of Sm3+ ions, which is ascribed to the progress of the presence of the localized surface Plasmon resonance (LSPR) indicating from the characteristic absorption peaks. The luminescence and absorption spectra have been discussed using a standard hypothesis Judd-Ofelt theory for a certain absorption transitions 6P3/2, 4I11/2, 6F11/2, 6F9/2, 6F7/2, 6F5/2, 6F3/2, 6H15/2, 6F1/2 and emission transitions 6H5/2, H7/2, 6H9/2 and H11/2 under 409 nm excitation of the Sm3+ ions. The decay life time curve exhibited a non-exponential behavior of the studied glass samples and the results were compared with the similar reported glasses. An efficient red and orange fluorescence emission illustrate that the Sm3+-doped sodium‑zinc tellurite embedded with Ag and Au NPs are potential materials for the laser illumination.
: 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.
Metal-free carbonaceous nanomaterials have witnessed a renaissance of interest due to the surge in the realm of nanotechnology. Among myriads of carbon-based nanostructures with versatile dimensionality, one-dimensional (1D) carbon nanotubes (CNTs) and zero-dimensional (0D) carbon dots (CDs) have grown into a research frontier in the past few decades. With extraordinary mechanical, thermal, electrical and optical properties, CNTs are utilized in transparent displays, quantum wires, field emission transistors, aerospace materials, etc. Although CNTs possess diverse characteristics, their most attractive property is their unique photoluminescence. On the other hand, another growing family of carbonaceous nanomaterials, which is CDs, has drawn much research attention due to its cost-effectiveness, low toxicity, environmental friendliness, fluorescence, luminescence and simplicity to be synthesized and functionalized with surface passivation. Benefiting from these unprecedented properties, CDs have been widely employed in biosensing, bioimaging, nanomedicine, and catalysis. Herein, we have systematically presented the fascinating properties, preparation methods and multitudinous applications of CNTs and CDs (including graphene quantum dots). We will discuss how CNTs and CDs have emerged as auspicious nanomaterials for potential applications, especially in electronics, sensors, bioimaging, wearable devices, batteries, supercapacitors, catalysis and light-emitting diodes (LEDs). Last but not least, this review is concluded with a summary, outlook and invigorating perspectives for future research horizons in this emerging platform of carbonaceous nanomaterials.
ntroduction: Nasopharyngeal carcinoma (NPC) is a prevalent cancer among human population in Southern China, Hong Kong and Southeast Asia. In Malaysia, NPC is the fourth most common cancer in both sexes, predominantly in the Chinese. Epstein-Barr virus (EBV) infection is known to be highly associated with NPC. Fibroblast growth factor receptor-4 (FGFR4) is part of the family of tyrosine kinase receptors that regulate cell survival, differentiation and pro-liferation. The binding of FGFR4 ligands such as fibroblasts growth factors (FGFs) has been shown to activate various oncogenic signalling pathway including MAPK, Ras and PI3K-Akt pathways. In the past, FGFR4 has been shown to promote tumorigenesis and tumour progression in various cancers such as liver, colon, breast and pancreatic and gastric cancers. However, its role in NPC establishment and pathogenesis is under-explored. This study aimed to evaluate the FGFR4 expression in NPC using various cell lines and its potential as a therapeutic target for NPC treat-ment by gene silencing. Methods: The basal FGFR4 level of NPC (EBV-positive: C666-1 and EBV-negative: HONE1 and HK1) and nasopharyngeal epithelial (NPE) normal (NP69 and NP460) cell lines was determined by western blot analysis and RT-qPCR. FGFR4 level at different time points (0, 24, 48, and 72 hours) in HONE1 and C666-1 cell lines were determined by western blot analysis. Luminescence-based assay was performed to determine the cell prolifer-ation of NPC cells in correlation with the FGFR4 expression. NPC cells were then treated with the optimised FGFR4 siRNA or FGFR inhibitor, BLU-9931 and the silencing/ inhibition of FGFR4 expression was confirmed by western blot analysis. The effect of FGFR4 inhibition on the cell proliferation and aggressiveness of NPC cells was then investigat-ed through wound healing assay and invasion marker analysis. Results: Out of the five tested cell lines, HONE1 and C666-1 highly expressed FGFR4, NP69 showed very low expression while HK1 and NP460 did not express FGFR4. In the time-point study, the FGFR4 level of HONE1 and C666-1 peaked at 24-48 hours which is the exponential phase of cells. Following that, the FGFR4 level decreased corresponding to the decreased cell growth rate due to the nutrient deprivation. siRNA experiments showed that 6.25nM of four siRNAs (5, 6, 9 and 10) could effectively target and silence the FGFR4 expression of HONE1, but not in C666-1 even up to 250nM was tested. When BLU-9931 was used, only modest inhibition was observed in both cells at 3uM. Compared to the untreated control, FGFR4-inhibited HONE1 exhibited decreased cell proliferation rate. Cell migration and invasion capabilities of HONE1 were also significantly reduced following the FGFR4 silencing, suggesting the potential of utilising FGFR4 as the therapeutic target. Conclusion: FGFR4 is highly expressed in C666-1 (EBV-positive) and HONE1 (initially EBV-positive, but lost EBV genome in subsequent in vitro passage) NPC cells, but not in EBV-negative HK1 NPC cell and normal NPE cells. FGFR4 gene silencing effectively inhibited the cell proliferation, migration and invasive potentials of NPC cell line. These findings highlight the therapeutic value of targeting FGFR4 for NPC treatment. Further investigations are war-ranted to reveal the molecular mechanism and the possible role of EBV in regulating FGFR4 pathway.
This study investigates the characteristics and application of the optically-stimulated luminescence dosimeter (OSLD) in cobalt-60 high dose rate (HDR) brachytherapy, and compares the results with the dosage produced by the treatment planning system (TPS). The OSLD characteristics comprised linearity, reproducibility, angular dependence, depth dependence, signal depletion, bleaching rate and cumulative dose measurement. A phantom verification exercise was also conducted using the Farmer ionisation chamber and in vivo diodes. The OSLD signal indicated a supralinear response (R2 = 0.9998). It exhibited a depth-independent trend after a steep dose gradient region. The signal depletion per readout was negligible (0.02%), with expected deviation for angular dependence due to off-axis sensitive volume, ranging from 1 to 16%. The residual signal of the OSLDs after 1 day bleached was within 1.5%. The accumulated and bleached OSLD signals had a standard deviation of ± 0.78 and ± 0.18 Gy, respectively. The TPS was found to underestimate the measured doses with deviations of 5% in OSLD, 17% in the Farmer ionisation chamber, and 7 and 8% for bladder and rectal diode probes. Discrepancies can be due to the positional uncertainty in the high-dose gradient. This demonstrates a slight displacement of the organ at risk near the steep dose gradient region will result in a large dose uncertainty. This justifies the importance of in vivo measurements in cobalt-60 HDR brachytherapy.
The performance of optically stimulated luminescence dosimeters (OSLDs, Al2O3:C) was evaluated in terms of the operational quantity of HP(10) in Co-60 external beam teletherapy unit. The reproducibility, signal depletion, and dose linearity of each dosimeter was investigated. For ten repeated readouts, each dosimeter exposed to 50mSv was found to be reproducible below 1.9 ± 3% from the mean value, indicating good reader stability. Meanwhile, an average signal reduction of 0.5% per readout was found. The dose response revealed a good linearity within the dose range of 5-50mSv having nearly perfect regression line with R2 equals 0.9992. The accuracy of the measured doses were evaluated in terms of operational quantity HP(10), wherein the trumpet curve method was used respecting the 1990 International Commission on Radiological Protection (ICRP) standard. The accuracy of the overall measurements from all dosimeters was discerned to be within the trumpet curve and devoid of outlier. It is established that the achieved OSL Al2O3:C dosimeters are greatly reliable for equivalent dose assessment.
Carbon-based quantum dots (C-QDs) were synthesized through microwave-assisted carbonization of an aqueous starch suspension mediated by sulphuric and phosphoric acids. The as-prepared C-QDs showed blue, green and yellow luminescence without the addition of any surface-passivating agent. The C-QDs were further analyzed by UV-vis spectroscopy to measure the optical response of the organic compound. The energy gaps revealed narrow sizing of C-QDs in the semiconductor range. The optical refractive index and dielectric constant were investigated. The C-QDs size distribution was characterized. The results suggested an easy route to the large scale production of C-QDs materials.
ZnO with two different morphologies were used to study the inhibition of Streptococcus sobrinus and Streptococcus mutans which are closely associated with tooth cavity. Rod-like shaped ZnO-A and plate-like shaped ZnO-B were produced using a zinc boiling furnace. The nanopowders were characterized using energy filtered transmission electron microscopy (EFTEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, Raman spectroscopy and dynamic light scattering (DLS) to confirm the properties of the ZnO polycrystalline wurtzite structures. XRD results show that the calculated crystallite sizes of ZnO-A and ZnO-B were 36.6 and 39.4nm, respectively, whereas DLS revealed particle size distributions of 21.82nm (ZnO-A) and 52.21nm (ZnO-B). PL spectra showed ion vacancy defects related to green and red luminescence for both ZnO particles. These defects evolved during the generation of reactive oxygen species which contributed to the antibacterial activity. Antibacterial activity was investigated using microdilution technique towards S. sobrinus and S. mutans at different nanopowder concentrations. Results showed that ZnO-A exhibited higher inhibition on both bacteria compared with ZnO-B. Moreover, S. mutans was more sensitive compared with S. sobrinus because of its higher inhibition rate.