UVA Region Research Articles

A “core-shell” structure imparting both gas barrier and UV shielding properties for a PLA/ PGA/ PBS ternary blend film

The core-shell structure enhances polymer blend systems by orderly assembly and leveraging complementary properties. This study aims to enhance the flexibility and barrier properties of polylactic acid (PLA, L) by blending it with polyglycolic acid (PGA, G) for gas barrier and polybutylene succinate (PBS, B) for flexibility. Encapsulating PGA in a core-shell structure using PBS resolves PGA's rapid hydrolysis issue. The theoretical models predicting dispersion patterns based on spreading coefficients and interfacial tensions were validated through SEM observations, confirming the formation of a core-shell structure in the 5L1G4B ternary blend. Compared to the PLA/PBS binary blend film, samples with PGA (5L1G4B and 4L1G5B) exhibit higher elongation at break and tearing strength. For instance, the elongation at break of the 5L1G4B sample increases from 272.3 % of 6L4B to 470.85 %. The 5L1G4B showed comparable oxygen and carbon dioxide barrier properties to the 6L4B sample. The 5L1G4B and 4L1G5B samples show <2 % UV transmittance in the UVA region, indicating excellent UV shielding. The 5L1G4B blend film, with its mechanical properties, oxygen barrier, UV resistance, and biodegradability, is ideal for outer layer packaging film and has the potential to replace LDPE in packaging juice and dairy product bottles.

Tandem Acylation and Aromatization of Vinylogous Esters: A Regiospecific Approach to Resorcinyl Ketones.

This study demonstrates the direct conversion of vinylogous esters into selectively protected 6-acyl resorcinols (4-alkoxy/aryloxy-2-hydroxy arylketones) in a regiospecific manner. Resorcinyl ketones are first-time synthesized, diverging from their traditional roots, originating from non-benzenoid pool materials. Converting cyclohexenones into phenol- or resorcinol-based arylketones remains challenging due to the stability and reactivity issues of intermediate products. Addressing this critical gap, we introduce a novel strategy: sequential one-pot acylation and oxidative aromatization of vinylogous esters. This innovative approach aims to surmount the long-standing barrier, facilitating the synthesis of diverse resorcinyl ketones. Furthermore, this method proves valuable for the synthesis of functionalized diaryl ethers and in the total synthesis of bioactive natural products and drug molecules such as angolensin, isoliquiritigenin, demethylsorbicillin, ponganone VII, and ipriflavone. It is also useful for modifying bioactive acids and alcohols by introducing a resorcinol functionality in the late stage of synthesis. Synthetic analogues of oxybenzone demonstrated superior ultraviolet (UV) absorption properties, effectively covering the entire UV-A and UV-B regions, spanning from 230 to 410 nm.

Allometric Models for Estimating Above-Ground, Below-Ground and Total Biomass of Tea (&lt;em&gt;Camellia sinensis&lt;/em&gt; (L.) O. Kuntze) Plants Grown in Uva and Up Country, Sri Lanka

This study was conducted to identify the dendrometric variables highly correlating with above-ground (AGB), below-ground (BGB) and total (TB) biomass of tea grown in Uva and Up Country Sri Lanka, develop allometric models to estimate AGB, BGB and TB of tea plants, and to investigate the applicability of already developed allometric models in other countries to Sri Lanka. Twelve experimental plots from TRIORCON field experiment at Tea Research Institute of Sri Lanka, and 18 farmer fields in Uva region, Sri Lanka were selected as the study sites. Representative tea plants were uprooted from the selected sites and seven dendrometric variables were measured. Fresh and dry AGB and BGB of the tea plants were determined. The best allometric models to predict AGB, BGB and TB using dendrometric variables were developed using multiple linear and non-linear regression analyses. Non-linear allometric models fitted best when predicting AGB and TB. Over 64% of total variability of AGB and TB was explained by these models using collar diameter at the soil level. Linear allometric fitted best when predicting BGB. Over 92% of total variability of BGB was explained by linear regression models using collar circumference, main-stem circumference, mean length and circumference at end of the primary branches. Leave-one-out cross validation showed strong positive (AGB and TB) and moderate positive (BGB) correlations between observed and predicted biomass values. Developed linear allometric models in comparison to those in literature showed better fit to data collected under Sri Lankan conditions and precisely estimated AGB, BGB and TB.

Cellular damage photosensitized by dasatinib, radical-mediated mechanisms and photoprotection in reconstructed epidermis

Dasatinib (DAS) is an anticancer drug employed in the treatment of certain hematological malignancies. Although DAS has been mainly developed for oral administration, it has recently garnered attention for its possible topical application. The use of topical drugs can cause photosensitivity, which is not listed as an adverse reaction for DAS. Since DAS absorbs UVA, it could potentially induce photosensitivity reactions and lead to oxidative damage to cellular targets. This study aims to investigate whether DAS exhibits phototoxic reactions on primary cellular targets in both solution and artificial skin, mimicking topical drug administration. It also examines the potential generation of highly reactive intermediates like organic radicals and ROS, which could trigger photosensitivity reactions. Upon DAS irradiation in the UVA region, the first transient species detected was the diradicaloid triplet excited state (3DAS∗) with an absorption maximum of around 490 nm, which was quenched by oxygen to produce singlet oxygen. Quenching experiments with linoleic acid and 3-methylindole indicated that radical-mediated (Type I) photosensitized damage to lipids and proteins is possible. However, the lack of triplet quenching with guanosine suggests that the Type II mechanism also plays a role in the photooxidation of biomolecules. Accordingly, the neutral red uptake phototoxicity test (photoirritation factor of 5) and the comet assay, revealed that this drug is photo(geno)toxic to cells. Moreover, investigations on lipid photoperoxidation, and protein and DNA photooxidation strongly support that different cellular compartments are potential targets for DAS-induced phototoxicity.Regarding its potential application in topical dermatological formulations, an O/W emulsion of DAS was prepared and tested in reconstructed human epidermis, and a significant phototoxicity was also demonstrated. Fortunately, this undesired side effect disappeared upon formulation of DAS along with a sunscreen. Thus, for topical treatments, the photosensitivity reactions induced by DAS can be prevented by using formulations including appropriate UVA filters.

Carbon dots as a distinctive platform fabricated through a sustainable approach for versatile applications

Red-emitting carbon dots (R-CDs) have garnered significant interest owing to its exceptional fluorescence (FL) characteristics. In this study, we present a one-pot solvothermal synthesis for producing biomass-derived R-CDs, utilizing Birch leaves as the primary raw material. The R-CDs display high solubility in ethanol and demonstrate deep-red emission at 625 nm with narrowband characteristics. After conducting a selectivity assessment with different metal ions, it is observed that R-CDs demonstrate exceptional sensitivity and specificity specifically to Fe3+. This demonstrates a linear relationship up to a concentration of 500 μM, with a detection limit of 0.302 μM (S/N=3). In this research, we created photoluminescent and transparent composites made from polyvinyl alcohol (PVA) with embedded fluorescent R-CDs, using the solution casting method for fabrication. The synthesized R-CDs exhibit robust and consistent FL in solution, whereas, the R-CDs@PVA nanocomposites (NCs) films are transparent and exceptionally flexible. The optimized 0.08 wt% R-CDs demonstrated the most effective ultra violet (UV) blockage across the UV-A (76.84 %), UV-B (74.86 %), and UV-C (78.46 %) region. However, PVA alone absorbed < 25 % of the light in all UV regions. The study explored the shape memory and FL characteristics of the R-CDs@PVA NCs changed under varying conditions such as water, temperature and pH. In alkaline conditions, the FL intensity of the R-CDs@PVA NCs increased due to the deprotonation of the R-CDs surface. In addition, R-CDs dispersed within PVA exhibit superior ink-free patterned substrates, proving to be advantageous for non-destructive template relief printing. Furthermore, R-CDs serve as effective anti-oxidants, combating 2,2-Diphenyl-1-picrylhydrazyl (DPPH) scavenging activity and mitigating the oxidative stress (OS) in red blood cells (RBCs) induced by sodium nitrite (NaNO2). They aid in the restoration of essential stress indicators, encompassing lipid peroxidation (LPO), protein carbonyl content (PCC), total thiol (TT), superoxide dismutase (SOD), and catalase (CAT). Furthermore, R-CDs restored the damaged liver, kidney, heart, and pancreas by regulating biochemical parameters. Furthermore, incorporated R-CDs into red light-emitting diodes (R-LEDs) and white light-emitting diodes (W-LEDs), thereby enhancing plant growth efficiency. The results of this study highlight the possible of R-CDs as non-toxic, UV blocking agents suitable for developing edible coatings and packaging. These properties suggest their applicability in the food industry, anti-counterfeiting (AC) measures, and biomedical applications.

Real-Time Ultraviolet Monitoring System with Low-Temperature Solution-Processed High-Transparent p-n Junction Photodiode with a Fast Responsive and High Rectification Ratio.

We introduce an enhanced performance organic-inorganic hybrid p-n junction photodiode, utilizing poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) and ZnO, fabricated through a solution-based process at a low temperature under 100 °C. Improved interfacial electronic structure, characterized by shallower Gaussian standard deviation of the density-of-state distribution and a larger interface dipole, has resulted in a remarkable fold increase of ∼102 in signal-to-noise ratio for the device. This photodiode exhibits a high specific detectivity (2.32 × 1011 Jones, ) and exceptional rectification ratio (5.47 × 104 at ±1 V). The primary light response, concentrated in the optimal thickness of the PTAA layer, contributes to response over the entire UVA region and rapid response speed, with rise and fall times of 0.24 and 0.64 ms, respectively. Furthermore, this work demonstrates immense potential of our device for health monitoring applications by enabling real-time and continuous measurements of UV intensity.

LOV1 protein of Pseudomonas cichorii JBC1 modulates its virulence and lifestyles in response to blue light

Bacteria perceive light signals via photoreceptors and modulate many physiological and genetic processes. The impacts played by light, oxygen, or voltage (LOV) and blue light (BL) photosensory proteins on the virulence-related traits of plant bacterial pathogens are diverse and complex. In this study, we identified LOV protein (Pc-LOV1) from Pseudomonas cichorii JBC1 (PcJBC1) and characterized its function using LOV1-deficient mutant (JBC1Δlov1). In the dark state, the recombinant Pc-LOV1 protein showed an absorption band in UV-A region with a double peak at 340 nm and 365 nm, and within the blue-region, it exhibited a main absorption at 448 nm along with two shoulder peaks at 425 nm and 475 nm, which is a typical feature of oxidized flavin within LOV domain. The adduct-state lifetime (τrec) of Pc-LOV1 was 67.03 ± 4.34 min at 25 °C. BL negatively influenced the virulence of PcJBC1 and the virulence of JBC1Δlov1 increased irrespective of BL, indicating that Pc-LOV1 negatively regulates PcJBC1 virulence. Pc-LOV1 and BL positively regulated traits relevant to colonization on plant surface, such as adhesion to the plant tissue and biofilm formation. In contrast, swarming motility, exopolysaccharide production, and siderophore synthesis were negatively controlled. Gene expression supported the modulation of bacterial features by Pc-LOV1. Overall, our results suggest that the LOV photosensory system plays crucial roles in the adaptive responses and virulence of the bacterial pathogen PcJBC1. The roles of other photoreceptors, sensing of other wavelengths, and signal networking require further investigation.

Systematic tuning of optical and electronic properties of holey graphene quantum dots for UV applications

Graphene quantum dots (GQDs) have remarkably demonstrated themselves as an efficient non-toxic material whose optoelectronic characteristics could be suitably tailored by molecular engineering. In present work, the properties of GQDs have been modified by creating pores in between them and then passivating them with H, F, and O atoms particularly finding their applications in the Ultraviolet (UV) region. For these purposes, materials having an emission wavelength in the UVA region are desirable. It has been investigated that these pores significantly altered the bandgap of GQDs which in turn affected their optical properties. Transitions contributing to the highest peaks in absorption and photoluminescence spectra have been identified and their isosurface contour-maps have also been plotted to find out the nature of this transition. Emission-wavelengths of these holey GQDs have been discovered to fall in the desirable UVA range, which is perfectly suitable for their usage in UV A lamps, medical phototherapy.

Visible light triggers the formation of reactive oxygen species in monoclonal antibody formulations

Most monoclonal antibody formulations require the presence of a surfactant, such as polysorbate, to ensure protein stability. The presence of high concentrations of polysorbate have been shown to enhance photooxidation of certain protein drug products when exposed to visible light. The current literature, however, suggest that photooxidation of polysorbate only occurs when exposed to visible light in combination with UVA light. This is probable as peroxides present in polysorbate solutions can be cleaved homolytically in the UVA region. In the visible region, photooxidation is not expected to occur as cleavage of peroxides is not expected at these wavelengths.This report presents findings suggesting that the presence of one or more photosensitiser(s) in polysorbate must be a cause and is required to catalyse the aerobic oxidation of polysorbate solutions upon exposure to visible light. Our investigation aimed to clarify the mechanism(s) of polysorbate photooxidation and explore the kinetics and the identity of the generated radicals and their impact on monoclonal antibody (mAb) degradation. Our study reveals that when polysorbate solutions are exposed to visible light between 400 - 800 nm in the absence of proteins, discolouration, radical formation, and oxygen depletion occur. We discuss the initial formation of reactive species, most likely occurring directly after reaction of molecular oxygen, with the presence of a triplet state photosensitiser, which is generated by intersystem crossing of the excited singlet state. When comparing the photooxidation of PS20 and PS80 in varying quality grades, we propose that singlet oxygen possesses potential for reacting with unsaturated fatty acids in PS80HP, however, PS20HP itself exhibited no measurable oxidation under the tested conditions. The study’s final part delves into the photooxidation behaviour of different PS grades, examining its influence on the integrity of a mAb in the formulation. Finally, we examined the effect of photooxidation on the integrity of monoclonal antibodies. Our findings show that the exposure to visible light in polysorbate-containing mAb solutions at high PS concentrations of 4 mg·ml−1 results in increased monoclonal antibody degradation, highlighting the need for cautious evaluation of the correct PS concentration to stabilise protein therapeutics.

La3+-adjusted optical and ligand field parameters in low CoO impurities Na2O–ZnO borate glass matrix

The effect of La2O3 on the ligand field and optical properties of the current glass system was investigated. In detail, the absorption band at (493–499 nm) is ascribed to 4T1g (F) → 2T1g (H) transition of Co2+ in octahedral symmetry. The absorption band at (574–580 nm) is ascribed to 4A2 (4F)→4T1(4P) transitions of Co2+ in tetrahedral symmetry. On the other hand, the electronic transition at (639–644 nm) is attributed to 5T2g→ 5Eg transition of Co3+ in octahedral symmetry. Moreover, the redshift of the absorption edges reduces the optical bandgaps from 3.42 eV to 3.24 eV. Additionally, the La2O3-free glass sample exhibited a transition at ∼230 nm in the UVC region. However, this glass sample showed an displayed transparency in the UVA and UVB regions. Furthermore, the redshift of the absorption edges resulted in the glass sample with the highest La2O3 content (i.e., 8 mol%) becoming UVA transparent while blocking UVC and UVB regions. The obtained data regarding the ligand field parameters indicate an increase in the ligand field splitting (10Dq), reflecting the increased interplay strength between Co2+ in tetrahedral symmetry and its ligands. Also, the values of the nonlinear refractive index and nonlinear optical parameters increased due to the enhancement of basicity within the glass network. These findings suggest that the glass with the greatest concentration has the potential to be utilized as an optical filter that allows UVA while blocking UVC and UVB electromagnetic waves.

Effect of Light Sources on Transmittance of Commercially Available Contact Lenses.

Previous studies have suggested that light rays may interact with contact lenses, potentially affecting their transmittance. This study aimed to investigate the effects of visible and ultraviolet (UV)-A light sources on the transmittance of some commercially available daily, weekly, and monthly contact lenses. Nine commercially available soft contact lenses were irradiated with a solar simulator, light-emitting diode (LED) source, laser source, and UV-A source. The average transmittance of the tested lenses before and after irradiation in the UV, visible, and infrared light wavelength ranges was determined using an Agilent UV-visible spectrophotometer, model 8453. The results showed a partial or complete block of UV transmission at the UV-B region (300 nm) and the UV-A region (355 nm) by the Bio true daily contact lens, as well as the Acuvue Oasys, Avaira, and Biomedics 55 weekly lenses. At the visible region (555 nm), irradiation of the contact lenses by different light sources resulted in reduced light transmittance. At the infrared region (900 nm), the weekly and monthly contact lenses partially blocked infrared transmission, while the daily lenses showed either increased or decreased infrared transmission. Solar and artificial lighting, as well as high-powered lasers, constitute a major concern on the contact lenses' light transmission and optical properties. It is essential to develop soft contact lenses that have photoprotective properties while maintaining visible light transmittance.

Optical, Structural, and Dielectric Characteristics of Flexible PVA/PEG/ZnMn2O4/CuCo2O4/x wt % Melanin Blended Polymer Composites

Our research described in the current paper was aimed to alter the optical and dielectric characteristics of polyvinyl alcohol/polyethylene glycol blended polymers by incorporating different quantities of melanin and ZnMn2O4/CuCo2O4 to create flexible blended polymer composites suitable for applications like photocatalysis, capacitors, and different optoelectronic applications. The PVA/PEG/ZnMn2O4/CuCo2O4-x wt % melanin blended polymer composites were created using a casting technique. The structural properties of the fillers and various blends were investigated using an X-ray diffraction technique. A transmittance electron microscope was used to investigate the features of the ZnMn2O4/CuCo2O4. The optical properties of the PVA/PEG/ZnMn2O4/CuCo2O4-x wt % melanin blend composites, which included their linear and nonlinear optical parameters, were analyzed using a diffused reflectance technique. The direct and indirect optical energy gaps attained their lowest values (5.47, 3.22, and 2.97) and (5, 1.18) eV in PVA/PEG/ZnMn2O4/CuCo2O4 blended polymer. The doped blends exhibited superior absorbance efficiency in the UV spectra in both the UVA and UVB regions. In the UV and visible ranges doped blends with 15 and 10 wt % of melanin had the highest refractive index values, respectively. The highest dielectric constant and electric ac conductivity were achieved as the blend was loaded with 5 wt % melanin. The energy density value of the doped blend containing 10% melanin was the highest when compared to other doped melanin polymers. The maximum height electrical potential barrier of each blend was also calculated. The electric modulus was also studied. The intensities of the emission peaks in terms of fluorescence characteristics were reduced as the PVA/PEG blend was loaded with ZnMn2O4/CuCo2O4-x wt % melanin. In conclusion, the PVA/PEG/ZnMn2O4/CuCo2O4-x wt % melanin blended polymer composites are promising hybrid materials for use in a variety of applications.

Band Gap Modulation in Zn2TiO4 Spinels for Efficient UV-A Persistent Luminescence

Spinels are important materials for an application in bioimaging. The key advantage with spinel-type hosts is the presence of antisite defects, which act as charge reservoirs for trapping electrons and holes at complementary defect sites. This makes them a host system similar to a molecular system. Herein, we present a systematic approach to modulating the band gap of an inverse Zn2TiO4 spinel. With a change in ZnO concentration, the absorption band at 375 nm diminishes and disappears at a ZnO:TiO2 concentration of 1.40:1.00. The band gap of the material is modified from 3.30 to 4.40 eV. The crystal structure of the sample does not change drastically as determined using X-ray diffraction and Rietveld refinement. The Zn2TiO4 emits in the UV-A region with a lifetime in the time domain of `ns’. The sample also shows persistent luminescence of at least 15 min upon excitation with 254 nm with prominent emission in the UV-A region (300–390 nm). The present results open a new avenue for the synthesis of spinel hosts where the band gap can be modified with ease. The UV emission thus observed is expected to find usage in interesting applications like photocatalysis, anti-counterfeiting, water disinfecting, etc.

Synthesis and characterization of α-(4-(2,3-hydroxylpropoxy)phenylimino)-o-cresol Schiff base as an effective UV-absorber for ink systems

Schiff base is a diverse group of organic compounds and has potential as a UV absorber for ink systems due to its high UV protection, simple synthesis, and high dispersion in organic matrices. In this work, a novel Schiff base α-(4-(2,3-dihydroxylpropoxy)phenylimino)-o-cresol (named GMA-I) was synthesized and investigated as a UV absorber for ink system. The UV-protection of GMA-I was evaluated on ink-coated duplex substrate samples via color measurement using an accelerated UV test chamber. The results showed that the GMA-I exhibited strong absorption in both UVA and UVB regions with an extra high molar absorption coefficient of 43,554 M−1 cm−1, and high thermal stability of 271.4 °C. Interestingly, the GMA-I showed high UV protection for ink platform at low content of 2 wt% thank to the intramolecular proton transfer mechanism and therefore potential as a UV absorber additive for ink systems.

Influence of the adsorption effect of graphene quantum dot on the photophysical properties and multiple antioxidant processes of gallic acid

In this work, the influence of graphene quantum dot (GQD) adsorption effect on the multiple antioxidant processes and photophysical properties of gallic acid (GA) has been investigated by density functional theory. Simulated absorption spectra of the GA-GQD covered UVA and UVB regions, and its extremely weak fluorescence intensity means that it is more suitable for use as the sunscreen than GA. Moreover, in the S0 state, the sequence of multiple antioxidant processes of GA (GA-GQD) is: e- → H3+ → e- → H1+ (e- → H2+ → e- → H3+), and the first step of antioxidant processes of GA-GQD is more straightforward to occur than GA according to the specific thermodynamic parameters. Furthermore, the dynamic simulations of GA and GA-GQD reacted with free radical ·OH revealed that their antioxidant processes are spontaneous, verifying their outstanding antioxidant abilities.

Super long ultraviolet-A persistent luminescence and photo-stimulated luminescence from CaMgGeO4: Bi3+

Here, we have developed a novel ultra long ultraviolet-A afterglow material CaMgGeO4: Bi3+, which shows more than 24 h UVA afterglow emission peaked at 346 nm. The crystal structure shows that the prepared sample is a pure phase with an orthogonal system of Pmnb space group. The composition of valence band and conduction band was analyzed by the density of states, which reveals that the bandgap of the CaMgGeO4 matrix is 3.69 eV. The photoluminescence spectrum of the sample consists of a broadband in the 320–400 nm UVA region, which belongs to the 3P1 → 1S0 electron transition of Bi3+. More importantly, under the excitation of ultraviolet lamp for 3 min, CaMgGeO4: Bi3+ exhibited an UVA ultra long persistent luminescence (LPL) with a duration of more than 24 h, which afterglow emission intensity still reaches 1500 cps and is about 6 times of the background intensity. In addition, the UVA emission of CaMgGeO4: Bi3+ after 13 h day can be repeatedly by short periods of low-energy light sources stimulation. The thermoluminescence analysis indicates that the presence of shallow and deep traps is responsible for excellent UVA-LPL and photo-stimulate luminescence (PSL). The excellent LPL and PSL properties can prompt CaMgGeO4: Bi3+ phosphor to be widely used in the field of photodynamic therapy.

A calibration methodology for the novel radioluminescence detector systems

Radioluminescence mapping using well-characterized and optimized optical systems is an effective method for localizing contamination with alpha-emitting radionuclides. To apply this novel approach to radiological emergency management, nuclear safeguards, nuclear decommissioning, and nuclear forensics, an established traceability chain is required. This work presents the development and implementation of a novel calibration methodology to provide valuable information about, and confidence in, the performance of radioluminescence detection systems. The proposed calibration methodology is based on two complementary approaches: (a) application of well-characterized activity standards to establish a traceable relationship between radioluminescence intensity and alpha activity, and (b) use of all optical radiation-based devices that, when calibrated against an alpha activity standard, simulate the radioluminescence induced in nitrogen (N2) and nitric oxide (NO) gases by alpha particles in specific spectral regions. A dedicated 210Po alpha activity standard with a narrow peak of less than 32keV FWHM at 5.3MeV has been developed and used to characterize a lens-based radioluminescence detection system in terms of its sensitivity to alpha-induced radioluminescence in different atmospheres (air, N2, N2 ＋ NO mixture) in the UV-A and UV-C (solar blind) spectral regions. The characterized lens system was then used as an intermediary transfer device to cross-calibrate two portable integrating sphere-based radiance standards designed to simulate radioluminescence in the UV-A and UV-C spectral regions. Both radiance standards can be used as transfer standards simulating up to 510MBq when used in the UV-A and up to 8.7GBq when used in the UV-C spectral regions. They substantially simplify routine quality control of radioluminescence detection systems by eliminating the need for open alpha sources, which are always associated with strict radiation safety precautions. Furthermore, since radiance standards can operate in a wide range of intensities, linearity and detection limits of radioluminescence detectors can be readily determined. The design, construction, radiometric characterization, and calibration of dedicated transfer standards, as well as the development of new calibration procedures for radiometric traceability of radioluminescence detection systems, will enable appropriate accident and post-accident radiation measurements that will lead to more effective countermeasures and better protection of people, wildlife, and the environment.

Enhanced Visible Light Absorption in Heteroleptic Cuprous Phenanthrolines.

This work presents a series of Cu(I) heteroleptic 1,10-phenanthroline chromophores featuring enhanced UVA and visible-light-harvesting properties manifested through vectorial control of the copper-to-phenanthroline charge-transfer transitions. The molecules were prepared using the HETPHEN strategy, wherein a sterically congested 2,9-dimesityl-1,10-phenanthrolne (mesPhen) ligand was paired with a second phenanthroline ligand incorporating extended π-systems in their 4,7-positions. The combination of electrochemistry, static and time-resolved electronic spectroscopy, 77 K photoluminescence spectra, and time-dependent density functional theory calculations corroborated all of the experimental findings. The model chromophore, [Cu(mesPhen)(phen)]+ (1), lacking 4,7-substitutions preferentially reduces the mesPhen ligand in the lowest energy metal-to-ligand charge-transfer (MLCT) excited state. The remaining cuprous phenanthrolines (2-4) preferentially reduce their π-conjugated ligands in the low-lying MLCT excited state. The absorption cross sections of 2-4 were enhanced (εMLCTmax = 7430-9980 M-1 cm-1) and significantly broadened across the UVA and visible regions of the spectrum compared to 1 (εMLCTmax = 6494 M-1 cm-1). The excited-state decay mechanism mirrored those of long-lived homoleptic Cu(I) phenanthrolines, yielding three distinguishable time constants in ultrafast transient absorption experiments. These represent pseudo-Jahn-Teller distortion (τ1), singlet-triplet intersystem crossing (τ2), and the relaxed MLCT excited-state lifetime (τ3). Effective light-harvesting from Cu(I)-based chromophores can now be rationalized within the HETPHEN strategy while achieving directionality in their respective MLCT transitions, valuable for integration into more complex donor-acceptor architectures and longer-lived photosensitizers.

Reduction of CO2 in the presence of light via excited-state hydride transfer reaction in a NADPH-inspired derivative.

The photo-catalytic reduction of CO2 into chemical feedstocks using solar energy has attracted vast interest in environmental science because of global warming. Based on our previous study on the CO2 complex with one of the benzimidazoline (BI) derivatives, we explore the photochemical reduction of CO2 in one of the benzimidazoline derivatives (1,3-dimethyl-5,6-diol-2,3-dihydro-1H-benzimidazole) by quantum-chemical methods. Our results reveal that carbon dioxide can be reduced to formate (HCOO-) by a hydride transfer reaction in the excited state of this complex of benzimidazoline derivative and CO2. While the ground-state hydride transfer reaction in this complex exhibits a substantial barrier, a charge-transfer can occur in the first singlet excited state of the complex in the UV-A region (326 nm), and after overcoming a moderate barrier (∼0.4 eV) the system can have access to the products. The interaction with a polar solvent decreases further the barrier such that the reaction in dimethyl sulfoxide can proceed with a negligibly small barrier (∼0.1 eV) or in a nearly barrierless manner. Our results show that this benzimidazoline derivative may act as a catalyst in the photoreduction of CO2.

Evaluation of knowledge, attitudes, and practices of estate managers on food safety of black tea manufacturing in the Uva region of Sri Lanka

Sri Lankan black tea is renowned for its high quality and regarded as a brand that is chemically safe, ozone-friendly, and ethically acceptable with accountable stakeholders in the supply chain. Meantime, food safety has become one of the mandated food attributes that is heavily concern by stakeholders even at the estate level. Hence, this study aimed to determine the level of knowledge, attitudes, and practice (KAP) of managers at black tea manufacturing in the Uva region of Sri Lanka regarding basic food safety concerns. Data were collected from 30 respondents at 30 black tea manufacturing factories in the Uva region using a stratified random sampling technique. A pre-tested interviewer-administered questionnaire based on KAP of basic food safety was utilized and collected data were analyzed using descriptive analysis and correlation analysis. The study indicated that the mean percentage of knowledge was satisfactory (93.1%), and the mean score for attitudes and practices of food safety was 4.7±0.4 (X±SD) and 4.6±0.5 (X±SD), respectively. However, this study depicted that the knowledge of food safety influenced managers’ attitudes (0.421, P&lt;0.05) but not their food safety behaviour. Further, they believed that food safety management systems would be a means of directing their black tea to the international market (76.7%), while pledging the concerns of food safety (70%). However, it was depicted that constraints with food handlers (100%) and financial difficulties (73.3%) hugely affected the implementation of food safety management systems at the black tea manufacturing factories in the Uva region of Sri Lanka. Hence, this study suggests continuous, periodical but short training to sustain the practice of handling teas safely in the Uva region of Sri Lanka.