near-UV Radiation Research Articles

Photochemical phosphorus-enabled scaffold remodeling of carboxylic acids.

The excitation of carbonyl compounds by light to generate radical intermediates has historically been restricted to ketones and aldehydes; carboxylic acids have been overlooked because of high energy requirements and low quantum efficiency. A successful activation strategy would necessitate a bathochromic shift in the absorbance profile, an increase in triplet diradical lifetime, and ease of further functionalization. We present a single-flask transformation of carboxylic acids to acyl phosphonates that can access synthetically useful triplet diradicals under visible light or near-ultraviolet irradiation. The use of phosphorus circumvents unproductive Norrish type I processes, promoting selectivity that enables hydrogen-atom transfer reactivity. Use of this strategy promotes the efficient scaffold remodeling of carboxylic acids through various annulation, contraction, and expansion manifolds.

Surface chemical analysis and luminescent properties of La[formula omitted]O[formula omitted](BO[formula omitted])(PO[formula omitted])[formula omitted]: Sm[formula omitted] phosphor

In this study, we successfully synthesised a series of La7O6(BO3)(PO4)2 (LBPO): Sm phosphors. We conducted microstructural analysis of the doped samples using X-ray diffraction, comparing them with the host material. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were utilised to analyse the intermolecular chemical bonds and surface chemical states of the optimal LBPO:0.07 Sm3+ sample, respectively. Upon exposure to 404 nm near-ultraviolet irradiation, visible light emissions from Sm3+ transitions from 4G5/2 to 6H5/2, 6H7/2, and 6H9/2 were observed. The best doping concentration of Sm3+ is 0.07 mol, with content quenching attributed to energy transfer interactions. The optical band gap was determined theoretically and experimentally. Additionally, we measured the decay lifetime and photoluminescence properties, indicating the potential of the optimal LBPO:0.07 Sm3+ phosphor as a red component in solid-state lighting.

The time evolution of the ultraviolet habitable zone

ABSTRACT For stars hosting Circumstellar Habitable Zone (CHZ) exoplanets, we investigate the time evolution of their ultraviolet habitable zone (UHZ), the annular region around a star where an exoplanet could experience a suitable ultraviolet environment for the presence and emergence of life, and the possible intersection of the UHZ with the CHZ. To estimate their ultraviolet (UV) luminosity evolution, and therefore the evolution of their UHZ, we analyse Swift-UV/Optical telescope observations and adopt the near-UV luminosity evolutionary tracks derived using GALEX observations of young moving groups. We find that an intersection between CHZ and UHZ could exist (or have existed) around all stars of our sample at different epochs, except for the coldest M-dwarfs (temperature $\lesssim 2800$ K, e.g. Trappist-1). For hotter M-dwarfs the formation of ribonucleic acid precursors through cyanosulfidic chemistry triggered by near-UV radiation could occur during the first $\simeq$1–2 Gyr. The radial extension and time duration of the CHZ–UHZ intersection increase with the stellar effective temperature and the exoplanet atmospheric transmissivity at near-UV wavelengths. Within our sample, Proxima Centauri represents a golden target for the quest of life outside the Solar system because it experienced a long-lasting and more extended, compared to similar M-dwarfs, CHZ–UHZ intersection.

Experimental investigations of diacetylene ice photochemistry in Titan’s atmospheric conditions

Context. A large fraction of the organic species produced photochemically in the atmosphere of Titan can condense to form ice particles in the stratosphere and in the troposphere. According to various studies, diacetylene (C4H2) condenses below 100 km where it can be exposed to ultraviolet radiation. Aims. We studied experimentally the photochemistry of diacetylene ice (C4H2) to evaluate its potential role in the lower altitude photochemistry of Titan’s atmospheric ices. Methods. C4H2 ice films were irradiated with near-ultraviolet (near-UV) photons (λ > 300 nm) with different UV sources to assess the impact of the wavelengths of photons on the photochemistry of C4H2. The evolution of the ice’s composition was monitored using spectroscopic techniques. Results. Our results reveal that diacetylene ice is reactive through singlet-triplet absorption, similar to the photochemistry of other organic ices of Titan (such as dicyanoacetylene C4N2 ice) that we investigated previously. Several chemical processes occurred during the photolysis: the hydrogenation of C4H2 to form other C4 hydrocarbons (vinylacetylene C4H4 to butane C4H10); the formation of larger and highly polymerizable hydrocarbons, such as triacetylene (C6H2); and the formation of an organic polymer that is stable at room temperature. Conclusions. The nondetection of diacetylene ice in Titan’s atmosphere or surface could be rationalized based on our experimental results that C4H2 is photochemically highly reactive in the solid phase when exposed to near-UV radiation that reaches Titan’s lower altitudes and surface. C4H2 may be one of the key molecules promoting the chemistry in the ices and aerosols of Titan’s haze layers, especially in the case of co-condensation with other organic volatiles, with which it could initiate more complex solid-phase chemistry.

Enhanced activation of sulfite by the iron-citrate complexes under NUV irradiation for metronidazole degradation: Kinetic, degradation mechanism and efficiency in real water

In the present study, a novel approach for the elimination of emerging pollutants through an advanced oxidation process has been developed by combining near ultraviolet (NUV) irradiation with an iron-citrate complex (Fe(III)-Cit) to overcome the defects of the traditional Fe(III)/sulfite system and enhance the activation of sulfite in a neutral aqueous solution. The performance of this system was studied using metronidazole (MTZ) as the target pollutant, and the impact of operational conditions such as initial pH, Fe(III)-Cit complex concentration, sulfite dose, metronidazole concentration and dissolved oxygen were studied. The rate constant of MTZ degradation at natural pH (7.0 ± 0.2) by the Fe(III)-Cit/sulfite/NUV system is over 12.72-times and 13.25-times higher than the sulfite/NUV and Fe(III)-Cit/NUV individual binary systems. The effectiveness of the system was further examined in various real water matrices. The latter proved to be effective in the following order: groundwater > ultra-pure water > > seawater, revealing that it was very effective in the former. Chemical probe experiments indicated that sulfate radicals and hydroxyl radicals were the principal reactive oxygen species involved in the photodegradation of MTZ. Additionally, dissolved oxygen played a crucial role in the reaction. MTZ degradation products were determined by HPLC/MS, leading to the identification of nine different by-products and the proposal of possible degradation pathways. Although further studies are required to better understand this system, this work paves the way for the application of activated sulfite-based processes for environmental remediation without pH adjustment, offering an alternative to the use of conventional oxidants.

JWST Reveals a Luminous Infrared Source at the Position of the Failed Supernova Candidate N6946-BH1

N6946-BH1 (BH1) is the first plausible candidate for a failed supernova (SN), a peculiar event in which a massive star disappears without the expected bright SN, accompanied by collapse into a black hole (BH). Following a luminous outburst in 2009, the source experienced a significant decline in optical brightness, while maintaining a persistent IR presence. While it was proposed to be a potential failed SN, such behavior has been observed in SN impostor events in nearby galaxies. Here, we present late-time observations of BH1, taken 14 yr after disappearance, using JWST’s NIRCam and MIRI instruments to probe a never before observed region of the object’s spectral energy distribution (SED). We show for the first time that all previous observations of BH1 (pre- and postdisappearance) are actually a blend of at least three sources. In the near-infrared, BH1 is notably fainter than the progenitor but retains similar brightness to its state in 2017. In the mid-infrared the flux appears to have brightened compared to the inferred fluxes from the best-fitting progenitor model. The total luminosity of the source is between 13% and 25% that of the progenitor. We also show that the IR SED appears consistent with polycyclic aromatic hydrocarbon features that arise when dust is illuminated by near-ultraviolet radiation. At present, the interpretation of BH1 remains uncertain. The observations match expectations for a stellar merger, but theoretical ambiguity in the failed SN hypothesis makes it hard to dismiss.

Near-ultraviolet radiation toward molecular cloud N4 in W 50/SS 433: Evidence for direct interaction of the jet with molecular cloud

Abstract We compared the molecular clouds in the western part of SS 433 with near-ultraviolet radiation data obtained from GALEX. Near-ultraviolet radiation is prominently confirmed toward only N4, while no near-ultraviolet radiation is detected toward N1, N2, or N3. The radiative region of near-ultraviolet radiation is nearly the same as the CO-emitting region in N4, and does not extend beyond the jet seen in X-ray radiation. Near-ultraviolet radiation cannot be explained solely by broad-band continuous radiation and may originate from line emissions. The intensity of near-ultraviolet radiation exhibits an anti-correlation with that of 13CO(J = 3–2) emission. This anti-correlation, along with strong far-infrared radiation in the region with weaker near-ultraviolet radiation intensity compared to its surroundings, suggests that near-ultraviolet radiation originates from behind the molecular cloud, heating up the interstellar dust in N4. Subsequently, the dust in N4 reradiates in the far-infrared band. In the same region, a high peak TMB ratio of 12CO(J = 3–2)$/$12CO(J = 1–0) of ∼0.9, and a high kinetic temperature of Tk ∼ 56 K in the molecular cloud, indicate that CO molecules are highly excited, and the molecular cloud is heated through photoelectric heating. This heating results from electrons released due to the photoelectric effect caused by the phenomenon where interstellar dust absorbs near-ultraviolet radiation. In terms of the timescale of near-ultraviolet radiation originating from line emissions, near-ultraviolet radiation towards N4 cannot be explained by the shock of the blast wave from a supernova that created W 50. These findings also suggest that N4 directly interacts with the jet from SS 433. As a result of this direct interaction, near-ultraviolet radiation is emitted from an interacting layer between the jet and N4.

A first-principles investigation of excitation and emission processes of CsI(Tl) under near-UV radiation

Based on the analyses of excitation paths in CsI(Tl) under near-UV light ( λmin = 220 nm), all possible excited states are modeled. The emission paths are revealed by the first-principles calculations performed for each excited state. Based on the analyses of band structure, density of states (DOS), and transition dipole moment (TDM), the theoretical range of central emission wavelength is proposed as 517 ∼ 538 nm for the Tl-center luminescence and 375 ∼ 405 nm for the intrinsic luminescence. This prediction agrees well with the experimental emission spectra, which have a peak at 514.2 nm and a shoulder at 410.6 nm. This method can be applied to CsI(Tl) under higher-energy radiation and other halide scintillator materials.

A Census of Near-UV M-dwarf Flares Using Archival GALEX Data and the gPHOTON2 Pipeline

M-dwarfs are common stellar hosts of habitable-zone exoplanets. Near-UV (NUV) radiation can severely impact the atmospheric and surface conditions of such planets, making the characterization of NUV flaring activity a key aspect in determining habitability. We use archival data from the Galaxy Evolution Explorer (GALEX) and XMM-Newton telescopes to study the flaring activity of M-dwarfs in the NUV. The GALEX observations form the most extensive data set of M-dwarfs in the NUV to date, with the exploitation of this data possible due to the new gphoton2 pipeline. We run a dedicated algorithm to detect flares in the pipeline-produced lightcurves and find some of the most energetic flares observed to date within the NUV bandpass, with energies of ∼1034 erg. Using GALEX data, we constrain flare frequency distributions for stars from M0-M6 in the NUV up to 105 s in equivalent duration and 1034 erg in energy, orders of magnitude above any previous study in the UV. We estimate the combined effect of NUV luminosities and flare rates of stars later than M2 to be sufficient for abiogenesis on habitable-zone exoplanets orbiting them. As a counterpoint, we speculate the high frequencies of energetic UV flares and associated coronal mass ejections would inhibit the formation of an ozone layer, possibly preventing the genesis of complex Earth-like life-forms due to sterilizing levels of surface UV radiation. We also provide a framework for future observations of M-dwarfs with ULTRASAT, a wide field-of-view NUV telescope to be launched in 2026.

Influence of photons of the near-ultraviolet radiation on the growth and development of sugar beet (<i>Beta vulgaris</i> L. ssp. <i>vulgaris var. saccharifera</i> Alef.) in a closed agrobiotechnosystem

Relevance and methodology. In order to determine the effect of near-ultraviolet radiation with a wavelength of 380 nm on the growth and development of a sugar beet hybrid plant, Smena was grown for 82 days under LED lighting with phytolamps and under conditions of increased UV-A intensity of the light range (an increase in the UV/PPFD ratio (0.027) compared with the control (0.0075) while maintaining the ratio of the remaining sites spectrum). The study was carried out on the basis of the digital software package "Synergotron" with a controlled internal environment.Results. An increase in the share of UV-A in the illumination spectrum leads to a significant change in the biometric indicators of plants – the aboveground biomass increases by 2.2 times compared to the control, and the mass of the underground part (root crops), on the contrary, decreases by 86.9%. At the same time, the share of root crops in the total biomass of plants decreases from 60% in the control to 30%. The morphological structure of the leaf apparatus changes: the proportion of petioles increases significantly compared to leaf blades (64.8% of petioles in aboveground biomass, whereas in the control 30%). Probably, an increase in the share of UV-A in the spectrum can favorably affect the cultivation of leaf forms of beets and other root crops. UV-A radiation leads to a change in the chemical composition of root crops, in particular, a decrease in the accumulation of dry substances (by 1.58%) and a decrease in sugar content (by 1.8%). An increase in the proportion of UV-A in the irradiation spectrum changes the parameters of chlorophyll fluorescence and contributes to an increase in the maximum quantum yield of Fv/Fm, non-photosynthetic quenching of NPQ fluorescence and a decrease in the real quantum yield of photosynthesis Y(II), as well as the electron transport rate (ETR).

Near-ultraviolet irradiation to stimulate unmodified polyether ether ketone to achieve stable and sustainable antibacterial activity

ObjectivesThis study aims to investigate the cytotoxicity and sustainable antibacterial activity of unmodified PEEK under specific wavelength light treatment (365 nm), and its antibacterial mechanism was also preliminarily discussed. MethodsA near-ultraviolet source with a wavelength of 365 nm and a power of 5 W were selected. The irradiation time was 30 min, and the distance was 100 mm. A water contact angle tester was used to characterize the surface of the PEEK after 1–15 light treatments. MC3TC-E1 cells were used to evaluate the cytotoxicity of the materials under light treatment. Five kinds of common oral bacteria were detected in vitro, and antibacterial efficiency was determined by colony-forming unit (CFU) and scanning electron microscope (SEM). The antibacterial mechanism of PEEK under light was preliminarily discussed by spectrophotometry. The membrane rupture of Staphylococcus aureus and Escherichia coli was detected by lactate dehydrogenase. Staphylococcus aureus and Staphylococcus mutans were selected for the cyclic antibacterial test. Statistical analysis was performed by one-way analysis of variance and Tukey multiple range test. A significance level of 0.05 was considered (α = 0.05). ResultsThe results of the cell experiment showed that PEEK had no cytotoxicity (P > 0.05). CFU results showed that PEEK had an obvious antibacterial effect on Staphylococcus aureus, Staphylococcus mutans, Staphylococcus gordonii and Staphylococcus sanguis, but had no antibacterial effect on Escherichia coli (P < 0.05). The SEM results also verified the above antibacterial effect. The existence of singlet oxygen was confirmed by spectrophotometry. Meanwhile, the rupture of Staphylococcus aureus membrane was verified by lactate dehydrogenase assay. The water contact angle of the PEEK surface did not change significantly after 15 cycles of light treatment. Cyclic antibacterial experiments showed that the antibacterial effect was sustainable. ConclusionsThis study showed that PEEK has good cytocompatibility with stable and sustainable antibacterial properties under near-ultraviolet. It provides a new idea to solve the non-antibacterial property of PEEK, and also provides a theoretical basis for its further application in dentistry.

Dynamics of Hydrogen Bond Breaking Induced by Outer-Valence Intermolecular Coulombic Decay

The photoexcitation of weakly bound complexes can lead to several decay pathways, depending on the nature of the potential energy surfaces. Upon excitation of a chromophore in a weakly bound complex, ionization of its neighbor upon energy transfer can occur due to a unique relaxation process known as intermolecular Coulombic decay (ICD), a phenomenon of renewed focus owing to its relevance in biological systems. Herein, we report the evidence for outer-valence ICD induced by multiphoton excitation by near-ultraviolet radiation of 4.4 eV photons, hitherto unknown in molecular systems. In the binary complexes of 2,6-difluorophenylacetylene with aliphatic amines, a resonant two-photon excitation localized on the 2,6-difluorophenylacetylene chromophore results in the formation of an amine cation following an outer-valence ICD process. The unique trends in experimentally observed translational energy distribution profiles of the amine cations following hydrogen bond dissociation, analyzed with the help of electronic structure and ab initio molecular dynamics calculations, revealed the presence of a delicate interplay of roaming dynamics, methyl-rotor dynamics, and binding energy.

Photocatalytic Activity and Stability of Organically Modified Layered Perovskite-like Titanates HLnTiO4 (Ln = La, Nd) in the Reaction of Hydrogen Evolution from Aqueous Methanol

Two series of hybrid inorganic–organic materials, prepared via interlayer organic modification of protonated Ruddlesden–Popper phases HLnTiO4 (Ln = La, Nd) with n-alkylamines and n-alkoxy groups of various lengths, have been systematically studied with respect to photocatalytic hydrogen evolution from aqueous methanol under near-ultraviolet irradiation for the first time. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample, its actual volume concentration in the suspension, pH of the medium and stability of the photocatalytic material under the operating conditions. The insertion of the organic modifiers into the interlayer space of the titanates allowed obtaining new, more efficient photocatalytic materials, being up to 68 and 29 times superior in the activity in comparison with the initial unmodified compounds HLnTiO4 and a reference photocatalyst TiO2 P25 Degussa, respectively. The hydrogen evolution rate over the samples correlates with the extent of their interlayer hydration, as in the case of the inorganic–organic derivatives of other layered perovskites reported earlier. However, the HLnTiO4-based samples demonstrate increased stability with regard to the photodegradation of the interlayer organic components as compared with related H2Ln2Ti3O10-based hybrid materials.

Modulating Optoelectronic and Elastic Properties of Anatase TiO2 for Photoelectrochemical Water Splitting

Titanium dioxide (TiO2) has been investigated for solar-energy-driven photoelectrical water splitting due to its suitable band gap, abundance, cost savings, environmental friendliness, and chemical stability. However, its poor conductivity, weak light absorption, and large indirect bandgap (3.2 eV) has limited its application in water splitting. In this study, we precisely targeted these limitations using first-principle techniques. TiO2 only absorbs near-ultraviolet radiation; therefore, the substitution (2.1%) of Ag, Fe, and Co in TiO2 significantly altered its physical properties and shifted the bandgap from the ultraviolet to the visible region. Cobalt (Co) substitution in TiO2 resulted in high absorption and photoconductivity and a low bandgap energy suitable for the reduction in water without the need for external energy. The calculated elastic properties of Co-doped TiO2 indicate the ductile nature of the material with a strong average bond strength. Co-doped TiO2 exhibited fewer microcracks with a mechanically stable composition.

The ultraviolet habitable zone of exoplanets

ABSTRACT The dozens of rocky exoplanets discovered in the circumstellar habitable zone (CHZ) currently represent the most suitable places to host life as we know it outside the Solar system. However, the presumed presence of liquid water on the CHZ planets does not guarantee suitable environments for the emergence of life. According to experimental studies, the building blocks of life are most likely produced photochemically in presence of a minimum ultraviolet (UV) flux. On the other hand, high UV flux can be life-threatening, leading to atmospheric erosion and damaging biomolecules essential to life. These arguments raise questions about the actual habitability of CHZ planets around stars other than Solar-type ones, with different UV to bolometric luminosity ratios. By combining the ‘principle of mediocrity’ and recent experimental studies, we define UV boundary conditions (UV-habitable zone, UHZ) within which life can possibly emerge and evolve. We investigate whether exoplanets discovered in CHZs do indeed experience such conditions. By analysing Swift-UV/Optical Telescope data, we measure the near ultraviolet (NUV) luminosities of 17 stars harbouring 23 planets in their CHZ. We derive an empirical relation between NUV luminosity and stellar effective temperature. We find that 18 of the CHZ exoplanets actually orbit outside the UHZ, i.e. the NUV luminosity of their M-dwarf hosts is decisively too low to trigger abiogenesis – through cyanosulfidic chemistry – on them. Only stars with effective temperature ≳3900 K illuminate their CHZ planets with enough NUV radiation to trigger abiogenesis. Alternatively, colder stars would require a high-energy flaring activity.

Mechanism for plasmon-generated solvated electrons

Solvated electrons are powerful reducing agents capable of driving some of the most energetically expensive reduction reactions. Their generation under mild and sustainable conditions remains challenging though. Using near-ultraviolet irradiation under low-intensity one-photon conditions coupled with electrochemical and optical detection, we show that the yield of solvated electrons in water is increased more than 10 times for nanoparticle-decorated electrodes compared to smooth silver electrodes. Based on the simulations of electric fields and hot carrier distributions, we determine that hot electrons generated by plasmons are injected into water to form solvated electrons. Both yield enhancement and hot carrier production spectrally follow the plasmonic near-field. The ability to enhance solvated electron yields in a controlled manner by tailoring nanoparticle plasmons opens up a promising strategy for exploiting solvated electrons in chemical reactions.

Flexible optoelectronic neural transistors with broadband spectrum sensing and instant electrical processing for multimodal neuromorphic computing

AbstractA flexible optoelectronic neural transistor (OENT) that consists of a one‐step spin‐coated tri‐blend film composed of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT), poly(3‐hexylthiophene‐2,5‐diyl) (P3HT), and poly(methyl methacrylate) (PMMA) is demonstrated. The C8‐BTBT and P3HT phases in the film partially segregate into distinct domains, which combine to provide broadband spectrum sensing, and instant electrical‐processing capabilities dominated by C8‐BTBT. The OENT is sensitive to solar radiation from the near‐ultraviolet (NUV) and to visible (Vis) radiation from blue to red. When exposed to NUV radiation, the OENT responds sensitively and retains the memory of the exposure for over 103 s. The OENT provides a warning of excessive chronic exposure to harmful NUV. These properties allow high‐pass filtering with different cut‐off frequencies fc that can restrict the reception of blue, green, or red. These switchable fc enables sensitive image reconstruction and multitarget monitoring. The device combined with a chitosan gel achieves strictly defined short‐range plasticity of &lt;1 s that can achieve diverse instant‐computing applications such as spatiotemporally correlated coding and logic functions. Stable real‐time signal processing facilitates the realization of a Morse‐code recognition system constructed using neuro‐morphological hardware, achieving highly accurate character recognition. This study provides a useful resource that can have applications in wearable biomedical electronics and multimodal neuromorphic computing.

Key Role Effect of Samarium in Realizing Zero Thermal Quenching and Achieving a Moisture-Resistant Reddish-Orange Emission in Ba3LaNb3O12:Sm3.

The strategy to enhance phosphor stability against thermal quenching and moisture conditions will contribute to controlling the feature of phosphor-converted white-light-emitting diodes (pc-WLEDs). Herein, an effective strategy is achieved with the incorporation of Sm3+ ions, and a robust reddish-orange emission (no thermal quenching up to 498 K) is obtained based on Ba3LaNb3O12 as a host. In light of excitation by near-ultraviolet irradiation at 408 nm, Ba3LaNb3O12:Sm3+ gives rise to a typical signal ascribed to the 4G5/2 → 6HJ/2 (J = 5, 7, 9, and 11) transitions of Sm3+ ions. The concentration quenching effect is observed when the Sm3+ content exceeds 10%, and the quenching mechanism is caused by electronic dipole-dipole interactions. Based on the narrow emission curves, a very high color purity (92.4%) could be recorded. The Sm3+ substitution at the Ba2+/La3+ site leads to a rigid structural lattice and abundant electron-trapping centers for the Sm3+ ions, which will be responsible for the zero-thermal-quenching phenomenon. In addition, oleic acid (OA) is selected to form a hydrophobic covering surface structure to protect Ba3LaNb3O12:Sm3+, which can assist in improving the moisture resistance. The most favorable parameters concerning the warm-light emission (a high general color rendering index, Ra, of 85.7 and a low correlated color temperature, CCT, of 4965 K) can be achieved in pc-WLEDs containing an OA-modified sample. Moreover, its luminous efficiency, LE, can maintain 82.9% of its initial value after 120 h under controlled environmental conditions of 85 °C and 85% humidity. These results pave a new way to optimize the sample as a potential candidate for red-emitting materials.

Effects of the sample matrix on the photobleaching and photodegradation of toluene-derived secondary organic aerosol compounds

Abstract. Secondary organic aerosol (SOA) generated from the photooxidation of aromatic compounds in the presence of oxides of nitrogen (NOx) is known to efficiently absorb ultraviolet and visible radiation. With exposure to sunlight, the photodegradation of chromophoric compounds in the SOA causes this type of SOA to slowly photobleach. These photodegradation reactions may occur in cloud droplets, which are characterized by low concentrations of solutes, or in aerosol particles, which can have highly viscous organic phases and aqueous phases with high concentrations of inorganic salts. To investigate the effects of the surrounding matrix on the rates and mechanisms of photodegradation of SOA compounds, SOA was prepared in a smog chamber by photooxidation of toluene in the presence of NOx. The collected SOA was photolyzed for up to 24 h using near-UV radiation (300–400 nm) from a xenon arc lamp under different conditions: directly on the filter, dissolved in pure water, and dissolved in 1 M ammonium sulfate. The SOA mass absorption coefficient was measured as a function of irradiation time to determine photobleaching rates. Electrospray ionization high-resolution mass spectrometry coupled to liquid chromatography separation was used to observe changes in SOA composition resulting from the irradiation. The rate of decrease in SOA mass absorption coefficient due to photobleaching was the fastest in water, with the presence of 1 M ammonium sulfate modestly slowing down the photobleaching. By contrast, photobleaching directly on the filter was slower. The high-resolution mass spectrometry analysis revealed an efficient photodegradation of nitrophenol compounds on the filter but not in the aqueous phases, with relatively little change observed in the composition of the SOA irradiated in water or 1 M ammonium sulfate despite faster photobleaching than in the on-filter samples. This suggests that photodegradation of nitrophenols contributes much more significantly to photobleaching in the organic phase than in the aqueous phase. We conclude that the SOA absorption coefficient lifetime with respect to photobleaching and lifetimes of individual chromophores in SOA with respect to photodegradation will depend strongly on the sample matrix in which SOA compounds are exposed to sunlight.

Amorphous calcium phosphate nanoparticles allow fingerprint detection via self-activated luminescence

Herein, stable activator-free photoluminescent nanoparticles based on amorphous calcium phosphate (ACP) were obtained for the first time, and their performance for latent fingerprint imaging was investigated. ACP nanoparticles with irregular rounded shape and diameters in 10–40 nm range were prepared by a rapid and simple chemical precipitation followed by heat treatment at 400 °C for 4 h. Notably, diffuse reflectance spectroscopy, photoluminescence excitation and emission measurements reveal a high density of localized energy states within the wide optical band gap of heat-treated ACP (Eg = 5.25–5.42 eV). This behavior allowed the excitation of ACP in near-ultraviolet region (λexc = 450 nm, 2.75 eV), leading to an intense defect-related broadband (490–890 nm) photoluminescence emission centered at 540 nm (2.30 eV), 50 times more intense than untreated nanoparticles. The effect of lattice shrinkage due to structural water elimination, the presence of ionic vacancies (VCa and VO in PO43-) and carbonate groups (CO32-), on the luminescent properties of ACP were discussed in detail, as well as investigated after aqueous-mediated ACP crystallization into hydroxyapatite (HA). ACP nanoparticles were non-cytotoxic, as determined by MTT assay in Human Dermal Fibroblast neonatal (HDFn) cell line, with cell viabilities superior to 95% in all tested concentrations (20–320 μg/mL), after incubation for 24 and 48 h. Latent fingerprint images were obtained using the ACP nanoparticles under near-ultraviolet irradiation (λexc = 450 nm) in tweezers and LCD smartphone and successfully validated by the Integrated Automated Fingerprint Identification System used by Scientific Police in Spain. The present results evidenced that the new luminescent ACP nanoparticles are safe to be used and agree with the forensic requirements for future legal actions.