Publication database
Roles of reactive oxygen species in UVA-induced oxidation of 5,6-dihydroxyindole-2-carboxylic acid-melanin as studied by differential spectrophotometric method
Eumelanin photoprotects pigmented tissues from ultraviolet (UV) damage. However, UVA-induced tanning seems to result from the photooxidation of preexisting melanin and does not contribute to photoprotection. We investigated the mechanism of UVA-induced degradation of 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-melanin taking advantage of its solubility in a neutral buffer and using a differential spectrophotometric method to detect subtle changes in its structure. Our methodology is suitable for examining the effects of various agents that interact with reactive oxygen species (ROS) to determine how ROS is involved in the UVA-induced oxidative modifications. The results show that UVA radiation induces the oxidation of DHICA to indole-5,6-quinone-2-carboxylic acid in eumelanin, which is then cleaved to form a photodegraded, pyrrolic moiety and finally to form free pyrrole-2,3,5-tricarboxylic acid. The possible involvement of superoxide radical and singlet oxygen in the oxidation was suggested. The generation and quenching of singlet oxygen by DHICA-melanin was confirmed by direct measurements of singlet oxygen phosphorescence.
Sensitive Water Probing through Nonlinear Photon Upconversion of Lanthanide-Doped Nanoparticles
Lanthanide-doped upconversion nanoparticles have received growing attention in the development of low-background, highly sensitive and selective sensors. Here, we report a water probe based on ligand-free NaYF4:Yb/Er nanoparticles, utilizing their intrinsically nonlinear upconversion process. The water molecule sensing was realized by monitoring the upconversion emission quenching, which is mainly attributed to efficient energy transfer between upconversion nanoparticles and water molecules as well as water-absorption-induced excitation energy attenuation. The nonlinear upconversion process, together with power function relationship between upconversion emission intensity and excitation power density, offers a sensitive detection of water content down to 0.008 vol % (80 ppm) in an organic solvent. As an added benefit, we show that noncontact detection of water can be achieved just by using water attenuation effect. Moreover, these upconversion nanoparticle based recyclable probes should be particularly suitable for real-time and long-term water monitoring, due to their superior chemical and physical stability. These results could provide insights into the design of upconversion nanoparticle based sensors.
Competition between recombination and extraction of free charges determines the fill factor of organic solar cells
Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter θ, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor:acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor:acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination.
Enhancement of objects in photoacoustic tomography using selective filtering
Here we developed a real-time photoacoustic tomography (PAT) imaging acquisition device based on the linear array transducer utilized on ultrasonic devices. Also, we produced a phantom including diverse contrast media and acquired PAT imaging as the light source wavelength was changing to see if the contrast media reacted. Indocyanine green showed the highest reaction around the 800-nm band, methylene blue demonstrated the same in the 750-nm band, and gold nanoparticle showed the same in the 700-nm band. However, in the case of superparamagnetic iron oxide, we observed not reaction within the wavelength bands used herein to obtain imaging. Moreover, we applied selective filtering to the acquired PAT imaging to remove noise from around and reinforce the object’s area. Consequentially, we could see the object area in the imaging was effectively detected and the image noise was removed.
Multi-photon quantum cutting in Gd2O2S:Tm3+ to enhance the photo-response of solar cells
Conventional photoluminescence (PL) yields at most one emitted photon for each absorption event. Downconversion (or quantum cutting) materials can yield more than one photon by virtue of energy transfer processes between luminescent centers. In this work, we introduce Gd2O2S:Tm3+ as a multi-photon quantum cutter. It can convert near-infrared, visible, or ultraviolet photons into two, three, or four infrared photons of ∼1800 nm, respectively. The cross-relaxation steps between Tm3+ ions that lead to quantum cutting are identified from (time-resolved) PL as a function of the Tm3+ concentration in the crystal. A model is presented that reproduces the way in which the Tm3+ concentration affects both the relative intensities of the various emission lines and the excited state dynamics and providing insight in the quantum cutting efficiency. Finally, we discuss the potential application of Gd2O2S:Tm3+ for spectral conversion to improve the efficiency of next-generation photovoltaics.
Optogenetic control of insulin secretion by pancreatic β-cells in vitro and in vivo
The present study assessed the ability of optogenetics techniques to provide a better understanding of the control of insulin secretion, particularly regarding pancreatic β-cell function in homeostasis and pathological conditions such as diabetes mellitus (DM). We used optogenetics to investigate whether insulin secretion and blood glucose homeostasis could be controlled by regulating intracellular calcium ion concentrations ([Ca2+]i) in a mouse pancreatic β-cell line (MIN6) transfected with the optogenetic protein channelrhodopsin-2 (ChR2). The ChR2-transfected MIN6 (ChR2-MIN6) cells secreted insulin following irradiation with a laser (470 nm). The increase in [Ca2+]i was accompanied by elevated levels of messenger RNAs that encode calcium/calmodulin-dependent protein kinase II delta and adenylate cyclase 1. ChR2-MIN6 cells suspended in matrigel were inoculated into streptozotocin-induced diabetic mice that were then subjected to a glucose tolerance test. Laser irradiation of these mice caused a significant decrease in blood glucose, and the irradiated implanted cells expressed insulin. These findings demonstrate the power of optogenetics to precisely and efficiently controlled insulin secretion by pancreatic β-cells ‘on demand', in contrast to techniques using growth factors or chemical inducers. Optogenetic technology shows great promise for understanding the mechanisms of glucose homeostasis and for developing treatments for metabolic diseases such as DM.
Transparent Organic Photodetector using a Near-Infrared Absorbing Cyanine Dye
Organic photodetectors are interesting for low cost, large area optical sensing applications. Combining organic semiconductors with discrete absorption bands outside the visible wavelength range with transparent and conductive electrodes allows for the fabrication of visibly transparent photodetectors. Visibly transparent photodetectors can have far reaching impact in a number of areas including smart displays, window-integrated electronic circuits and sensors. Here, we demonstrate a near-infrared sensitive, visibly transparent organic photodetector with a very high average visible transmittance of 68.9%. The transmitted light of the photodetector under solar irradiation exhibits excellent transparency colour perception and rendering capabilities. At a wavelength of 850 nm and at −1 V bias, the photoconversion efficiency is 17% and the specific detectivity is 1012 Jones. Large area photodetectors with an area of 1.6 cm2 are demonstrated.
Efficient charge generation by relaxed charge-transfer states at organic interfaces
Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.
Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells
Perovskite solar cells with submicrometre-thick CH3NH3PbI3 or CH3NH3PbI3–xClx active layers show a power conversion efficiency as high as 15%. However, compared to the best-performing device, the average efficiency was as low as 12%, with a large standard deviation (s.d.). Here, we report perovskite solar cells with an average efficiency exceeding 16% and best efficiency of 17%. This was enabled by the growth of CH3NH3PbI3 cuboids with a controlled size via a two-step spin-coating procedure. Spin-coating of a solution of CH3NH3I with different concentrations follows the spin-coating of PbI2, and the cuboid size of CH3NH3PbI3 is found to strongly depend on the concentration of CH3NH3I. Light-harvesting efficiency and charge-carrier extraction are significantly affected by the cuboid size. Under simulated one-sun illumination, average efficiencies of 16.4% (s.d. ± 0.35), 16.3% (s.d. ± 0.44) and 13.5% (s.d. ± 0.34) are obtained from solutions of CH3NH3I with concentrations of 0.038 M, 0.050 M and 0.063 M, respectively. By controlling the size of the cuboids of CH3NH3PbI3 during their growth, we achieved the best efficiency of 17.01% with a photocurrent density of 21.64 mA cm–2, open-circuit photovoltage of 1.056 V and fill factor of 0.741.
Luminescence upconversion in colloidal double quantum dots
Luminescence upconversion nanocrystals capable of converting two low-energy photons into a single photon at a higher energy are sought-after for a variety of applications, including bioimaging and photovoltaic light harvesting. Currently available systems, based on rare-earth-doped dielectrics, are limited in both tunability and absorption cross-section. Here we present colloidal double quantum dots as an alternative nanocrystalline upconversion system, combining the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. By tailoring its composition and morphology, we form a semiconducting nanostructure in which excited electrons are delocalized over the entire structure, but a double potential well is formed for holes. Upconversion occurs by excitation of an electron in the lower energy transition, followed by intraband absorption of the hole, allowing it to cross the barrier to a higher energy state. An overall conversion efficiency of 0.1% per double excitation event is achieved.