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.
Photobacterium species are Gram-negative coccobacilli which are distributed in marine habitats worldwide. Some species are unique because of their capability to produce luminescence. Taxonomically, about 23 species and 2 subspecies are validated to date. Genomes from a few Photobacterium spp. have been sequenced and studied. They are considered a special group of bacteria because some species are capable of producing essential polyunsaturated fatty acids, antibacterial compounds, lipases, esterases and asparaginases. They are also used as biosensors in food and environmental monitoring and detectors of drown victim, as well as an important symbiont.
Understanding the influence of co-dopants in the luminescence enhancement of carbonate glasses is the key issue in dosimetry. A series of borate glasses modified by lithium and potassium carbonate were synthesized by the melt-quenching method. The glass mixture activated with various concentrations of TiO2 and MgO was subjected to various doses of gamma-rays ((60)Co). The amorphous nature of the samples was confirmed by x-ray diffraction (XRD) spectra. The simple glowing curve of the glass doped with TiO2 features a peak at 230°C, whose intensity is maximal at 0.5 mol% of the dopant. The intensity of the glowing curve increases with the concentration of MgO added as a co-dopant up to 0.25 mol%, where it is two times higher than for the material without MgO thermoluminescence properties, including dose response, reproducibility, and fading were studied. The effective atomic number of the material was also determined. Kinetic parameters, such as kinetics order, activation energy, and frequency factor are estimated. The photoluminescence spectra of the titanium-doped glass consist of a prominent peaks at 480 nm when laser excitation at 650 nm is used. A three-fold photoluminescence enhancement and a blue shift of the peak were observed when 0.1% MgO was introduced. In addition, various physical parameters, such as ion concentration, polaron radius and internuclear distances were calculated. The mechanism for the thermoluminescence and photoluminescence enhancements are discussed.
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.
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.
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.
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.
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.
This study investigated the effects of combined minimal concentrations of quercetin and pioglitazone on angiotensin II-induced contraction of the aorta from fructose-streptozotocin (F-STZ)-induced type 2 diabetic rats and the possible role of superoxide anions (O2(-)) and nitric oxide (NO) in their potential therapeutic interaction. Contractile responses to Ang II of aortic rings from Sprague-Dawley (SD) and F-STZ rats were tested following pre-incubation of the tissues in the vehicle (DMSO; 0.05%), quercetin (Q, 0.1 μM), pioglitazone (P, 0.1 μM) or their combination (P + Q; 0.1 μM each). The amount of superoxide anion was evaluated by lucigenin-enhanced chemiluminescence and dihydroethidium fluorescence, and NO by assay of total nitrate/nitrite, and 4-Amino-5-Methylamino-2',7'-Difluorofluorescein (DAF-FM) diacetate. The synergistic reduction of Ang II-induced contraction of diabetic but not normal aorta with minimally effective concentrations of P + Q occurs through inhibiting O2(-) and increasing NO bioavailability. This finding opens the possibility of maximal vascular protective/antidiabetic effects with low dose pioglitazone combined with quercetin, thus minimizing the risk of adverse effects.
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.
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.
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.
In this study, we synthesized a multifunctional nanoparticulate system with specific targeting, imaging, and drug delivering functionalities by following a three-step protocol that operates at room temperature and solely in aqueous media. The synthesis involves the encapsulation of luminescent Mn:ZnS quantum dots (QDs) with chitosan not only as a stabilizer in biological environment, but also to further provide active binding sites for the conjugation of other biomolecules. Folic acid was incorporated as targeting agent for the specific targeting of the nanocarrier toward the cells overexpressing folate receptors. Thus, the formed composite emits orange-red fluorescence around 600 nm and investigated to the highest intensity at Mn(2+) doping concentration of 15 at.% and relatively more stable at low acidic and low alkaline pH levels. The structural characteristics and optical properties were thoroughly analyzed by using Fourier transform infrared, X-ray diffraction, dynamic light scattering, ultraviolet-visible, and fluorescence spectroscopy. Further characterization was conducted using thermogravimetric analysis, high-resolution transmission electron microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray fluorescence, and X-ray photoelectron spectroscopy. The cell viability and proliferation studies by means of MTT assay have demonstrated that the as-synthesized composites do not exhibit any toxicity toward the human breast cell line MCF-10 (noncancer) and the breast cancer cell lines (MCF-7 and MDA-MB-231) up to a 500 µg/mL concentration. The cellular uptake of the nanocomposites was assayed by confocal laser scanning microscope by taking advantage of the conjugated Mn:ZnS QDs as fluorescence makers. The result showed that the functionalization of the chitosan-encapsulated QDs with folic acid enhanced the internalization and binding affinity of the nanocarrier toward folate receptor-overexpressed cells. Therefore, we hypothesized that due to the nontoxic nature of the composite, the as-synthesized nanoparticulate system can be used as a promising candidate for theranostic applications, especially for a simultaneous targeted drug delivery and cellular imaging.
Chemiluminescence was evaluated as a diagnostic aid in the detection of oral cancer and potentially malignant epithelial lesions (PMELs) by comparing it against 1% tolonium chloride mouth rinse. Forty-six clinically identified lesions [14 primary squamous cell carcinoma (SCC), 26 PMELs and 6 benign lesions] and five cases of normal oral mucosa from 40 subjects (inclusive of 10 previously treated SCC cases) were examined with a commercial chemiluminescent kit (Vizilite) and tolonium chloride. Biopsy and histological verification of 31 lesions disclosed 14 SCC (45.2%), 10 epithelial dysplasias (32.3%), 5 lichen planus (16.1%) and 2 benign lesions (6.4%). For the remaining 15 lesions, a biopsy was not performed owing to patient's lack of consent or ill-health. The five cases of normal oral mucosa which tested negative for both tools were also not biopsied for ethical reasons. Sensitivity for Vizilite and tolonium chloride was 100% and 70.3%, respectively; and specificity was 14.2% for Vizilite and 25% for tolonium chloride. Their accuracy was 80.6% and 64.5%, respectively. Current findings suggest that chemiluminescence is a more reliable diagnostic tool than tolonium chloride in the detection of oral cancer and PMELs, and for follow-up of patients treated for the same.
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.
The rise in pollution cases globally is expected to increase in line with industrialization.
Monitoring activities for pollutants have been hampered by the astronomical costs of
instrumental-based approach. This has resulted in the intense research on low cost
biomonitoring systems using enzymes, organisms including microorganisms. Only positive
samples are sent for instrumental analysis; dramatically cutting the cost of instrumental
analysis. This review attempts to outline and give due recognition to several selected bioassay
systems that have been tested for their applicability using polluted water samples as a routine
first line-of-defense. This includes small aquatic organisms-based assays, enzymes especially
proteases and bacterial-based systems using respiratory dye or luminescence systems as a
method for toxicant detection.
A series of Zn(II)-Schiff bases I, II and III complexes were synthesized by reaction of o-phenylenediamine with 3-methylsalicylaldehyde, 4-methylsalicylaldehyde and 5-methylsalicylaldehyde. These complexes were characterized using FT-IR, UV-Vis, Diffuse reflectance UV-Vis, elemental analysis and conductivity. Complex III was characterized by XRD single crystal, which crystallizes in the triclinic system, space group P-1, with lattice parameters a=9.5444(2) Å, b=11.9407(2) Å, c=21.1732(3) Å, V=2390.24(7) Å(3), D ( c )=1.408 Mg m(-3), Z=4, F(000)=1050, GOF=0.981, R1=0.0502, wR2=0.1205. Luminescence property of these complexes was investigated in DMF solution and in the solid state. Computational study of the electronic properties of complex III showed good agreement with the experimental data.
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.
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.