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Red-emitting Mn⁴⁺-doped fluorides are a promising class of materials to improve the color rendering and luminous efficacy of white light-emitting diodes (w-LEDs). For w-LEDs, the luminescence quenching temperature is very important, but surprisingly no systematic research has been conducted to understand the mechanism for thermal quenching in Mn⁴⁺-doped fluorides. Furthermore, concentration quenching of the Mn⁴⁺ luminescence can be an issue but detailed investigations are lacking. In this work, we study thermal quenching and concentration quenching in Mn⁴⁺-doped fluorides by measuring luminescence spectra and decay curves of K₂TiF₆:Mn⁴⁺ between 4 and 600 K and for Mn⁴⁺ concentrations from 0.01% to 15.7%. Temperature-dependent measurements on K₂TiF₆:Mn⁴⁺ and other Mn⁴⁺-doped phosphors show that quenching occurs through thermally activated crossover between the ⁴T₂ excited state and ⁴A₂ ground state. The quenching temperature can be optimized by designing host lattices in which Mn⁴⁺ has a high ⁴T₂ state energy. Concentration-dependent studies reveal that concentration quenching effects are limited in K₂TiF₆:Mn⁴⁺ up to 5% Mn⁴⁺. This is important, as high Mn⁴⁺ concentrations are required for sufficient absorption of blue LED light in the parity-forbidden Mn⁴⁺ d–d transitions. At even higher Mn⁴⁺ concentrations (>10%), the quantum efficiency decreases, mostly due to direct energy transfer to quenching sites (defects and impurity ions). Optimization of the synthesis to reduce quenchers is crucial for developing more efficient highly absorbing Mn⁴⁺ phosphors. The present systematic study provides detailed insights into temperature and concentration quenching of Mn⁴⁺ emission and can be used to realize superior narrow-band red Mn⁴⁺ phosphors for w-LEDs.

Solid-state dye-sensitized solar cells currently suffer from issues such as inadequate nanopore filling, low conductivity and crystallization of hole-transport materials infiltrated in the mesoscopic TiO₂ scaffolds, leading to low performances. Here we report a record 11% stable solid-state dye-sensitized solar cell under standard air mass 1.5 global using a hole-transport material composed of a blend of [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)₂](bis(trifluoromethylsulfonyl)imide)₂ and [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)₂](bis(trifluoromethylsulfonyl)imide). The amorphous Cu(II/I) conductors that conduct holes by rapid hopping infiltrated in a 6.5 μm-thick mesoscopic TiO₂ scaffold are crucial for achieving such high efficiency. Using time-resolved laser photolysis, we determine the time constants for electron injection from the photoexcited sensitizers Y123 into the TiO₂ and regeneration of the Y123 by Cu(I) to be 25 ps and 3.2 μs, respectively. Our work will foster the development of low-cost solid-state photovoltaic based on transition metal complexes as hole conductors.

Time-resolved serial femtosecond crystallography using an X-ray free electron laser (XFEL) in conjunction with a photosensitive caged-compound offers a crystallographic method to track enzymatic reactions. Here we demonstrate the application of this method using fungal NO reductase, a heme-containing enzyme, at room temperature. Twenty milliseconds after caged-NO photolysis, we identify a NO-bound form of the enzyme, which is an initial intermediate with a slightly bent Fe-N-O coordination geometry at a resolution of 2.1 Å. The NO geometry is compatible with those analyzed by XFEL-based cryo-crystallography and QM/MM calculations, indicating that we obtain an intact Fe³⁺-NO coordination structure that is free of X-ray radiation damage. The slightly bent NO geometry is appropriate to prevent immediate NO dissociation and thus accept H⁻ from NADH. The combination of using XFEL and a caged-compound is a powerful tool for determining functional enzyme structures during catalytic reactions at the atomic level.

Photoacoustic Tomography (PAT) is a promising medical imaging modality that combines optical imaging contrast with the spatial resolution of ultrasound imaging. It can also distinguish the changes in biological features. But, real-time PAT system should be confirmed due to photoacoustic effect for tissue. Thus, we have developed a real-time PAT system using a custom-developed data acquisition board and ultrasound linear probe. To evaluate performance of our system, phantom test was performed. As a result of those experiments, the system showed satisfactory performance and its usefulness has been confirmed. We monitored the degradation of inflammation which induced on the rat’s kidney using real-time PAT.

Solar cells that operate efficiently under indoor lighting are of great practical interest as they can serve as electric power sources for portable electronics and devices for wireless sensor networks or the Internet of Things. Here, we demonstrate a dye-sensitized solar cell (DSC) that achieves very high power-conversion efficiencies (PCEs) under ambient light conditions. Our photosystem combines two judiciously designed sensitizers, coded D35 and XY1, with the copper complex Cu(II/I)(tmby) as a redox shuttle (tmby, 4,4′,6,6′-tetramethyl-2,2′-bipyridine), and features a high open-circuit photovoltage of 1.1 V. The DSC achieves an external quantum efficiency for photocurrent generation that exceeds 90% across the whole visible domain from 400 to 650 nm, and achieves power outputs of 15.6 and 88.5 μW cm^–2 at 200 and 1,000 lux, respectively, under illumination from a model Osram 930 warm-white fluorescent light tube. This translates into a PCE of 28.9%.

We report a target-enclosing, hybrid tomograph with a total of 768 elements based on capacitive micromachined ultrasound transducer technology and providing fast, high-resolution 2-D/3-D photoacoustic and ultrasound tomography tailored to finger imaging.A freely programmable ultrasound beamforming platform sampling data at 80 MHz was developed to realize plane wave transmission under multiple angles. A multiplexing unit enables the connection and control of a large number of elements. Fast image reconstruction is provided by GPU processing. The tomograph is composed of four independent and fully automated movable arc-shaped transducers, allowing imaging of all three finger joints. The system benefits from photoacoustics, yielding high optical contrast and enabling visualization of finger vascularization, and ultrasound provides morphologic information on joints and surrounding tissue. A diode-pumped, Q-switched Nd:YAG laser and an optical parametric oscillator are used to broaden the spectrum of emitted wavelengths to provide multispectral imaging. Custom-made optical fiber bundles enable illumination of the region of interest in the plane of acoustic detection. Precision in positioning of the probe in motion is ensured by use of a motor-driven guide slide. The current position of the probe is encoded by the stage and used to relate ultrasound and photoacoustic signals to the corresponding region of interest of the suspicious finger joint. The system is characterized in phantoms and a healthy human finger in vivo. The results obtained promise to provide new opportunities in finger diagnostics and establish photoacoustic/ultrasoundtomography in medical routine.

Biomedical imaging used for medical diagnosis constantly requires improvement in the characteristics for imaging devices. The sensing devices are one of the most important pieces to improve in order to get images with better quality. In this thesis, it is proposed the use of interferometric fiber-optic sensors (which offer the advantages inherent to optical fibers) as devices to detect pressure/acoustic signals generated by the photoacoustic effect. It is explored the capability of using fiber-optic interferometric hydrophones in order to determine the thickness of a material derived from the acoustic signal generated when a sample is illuminated. In addition, the analysis of photoacoustic signals generated by the excitation of nanoparticles of an anisotropic material as absorption centers. Finally, the cross-section of a metallic sample was photoacoustically imaged by acquiring the pressure signals generated.

Photoacoustic imaging has emerged as a promising technique to improve preclinical and clinical imaging by providing users with label-free optical contrast of tissue. Here, we present a proof-of-concept study for noninvasive in vivo murine lipid imaging using 1210 nm light to investigate differences in periaortic fat among mice of different gender, genotypes, and maturation. Acquired lipid signals suggest that adult male apoE^−/− mice have greater periaortic fat accumulation compared to adolescent males, apoE^−/− females, and wild-type mice. These results demonstrate the potential of photoacoustic tomography for studying vascular pathophysiology and improving the diagnosis of lipid-based diseases.

We present infrared multiple photon dissociation (IRMPD) spectra of (H₂O)_nO˙⁻ and (H₂O)_nOH⁻ cluster ensembles for ñ ≈ 8 and 47 in the range of 2400–4000 cm⁻¹. Both hydrated ions exhibit the same spectral features, in good agreement with theoretical calculations. Decomposition of the calculated spectra shows that bands originating from H₂O⋯O˙⁻ and H₂O⋯OH⁻ interactions span almost the whole spectral region of interest. Experimentally, evaporation of OH˙ is observed to a small extent, which requires interconversion of (H₂O)_nO˙⁻ into (H₂O)_n–1OH˙OH⁻, with subsequent H₂O evaporation preferred over OH˙ evaporation. The modeling shows that (H₂O)_nO˙⁻ and (H₂O)_n–1OH˙OH⁻ cannot be distinguished by IRMPD spectroscopy.

The risk of chronic oxidative stress in the retinal pigment epithelium (RPE) increases with age due to accumulation of the photoreactive age pigment lipofuscin (LFG). Here, we asked whether sublethal and weakly lethal photic stress, induced by irradiation of ARPE-19 cells containing phagocytised LFG, affected the cell specific phagocytic activity, which is critically important for proper functioning and survival of the retina, and if natural antioxidants could modify the observed outcomes. ARPE-19 cells preloaded with LFG isolated from human donors of different age or containing LFG enriched with zeaxanthin and α-tocopherol (LFG-A), were irradiated with blue light. Phagocytosis of fluorescein-5-isothiocyanate (FITC)-labelled photoreceptor outer segments was determined by flow cytometry. Photoreactivity of LFG and LFG-A was analysed by measuring photoconsumption of oxygen and photogeneration of singlet oxygen mediated by the granules. LFG-mediated photic stress in ARPE-19 cells induced significant inhibition of their specific phagocytosis. The inhibitory effect increased with age of LFG donors and was reduced by enrichment of the granules with antioxidants. Oxygen consumption and generation of singlet oxygen induced by the photoexcited LFG increased with donor’s age and was partially quenched by antioxidants. Although the phototoxic potential of lipofuscin increased with age, natural antioxidants reduced photoreactivity of LFG and their efficiency to induce oxidative stress. This study has demonstrated, for the first time, that mild oxidative stress, mediated by the age pigment lipofuscin, impairs specific phagocytic activity of RPE, and that natural antioxidants can protect this important cellular function by reducing lipofuscin photoreactivity.