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At least 613 records · Page 34

Influence of silver nanoparticles on relaxation processes and efficiency of dipole – dipole energy transfer between dye molecules in polymethylmethacrylate films

The fluorescence and phosphorescence of dyes in thin polymethylmethacrylate (PMMA) films in the presence of ablated silver nanoparticles has been investigated in a wide temperature range by methods of femtosecond and picosecond laser photoexcitation. The fluorescence and phosphorescence times, as well as spectral and kinetic characteristics of rhodamine 6G (R6G) molecules in PMMA films are measured in a temperature range of 80 – 330 K. The temperature quenching activation energy of the fluorescence of R6G molecules in the presence of ablated silver nanoparticles is found. The vibrational relaxation rate of R6G in PMMA films is estimated, the efficiency of the dipole – dipole electron energy transfer between R6G and brilliant green molecules (enhanced by plasmonic interaction with ablated silver nanoparticles) is analysed, and the constants of this energy transfer are determined. (nanophotonics)

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO 2 /TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3 H 2 ) 2 bpy) 2 Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2 )] 4+ ([RuaII-RubII-OH 2 ] 4+ , combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2 O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO 2 /TiO 2 |-[Ru a II -Ru b II -OH 2 ] 4+ (Al 2 O 3 or TiO 2 ) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H 2 and O 2 . The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2 /TiO 2 core/shell compared with nanoITO/TiO 2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm 2 with 445-nm, ~90-mW/cm 2 illumination in a phosphate buffer at pH 7.

36 MATERIALS SCIENCE↗

Shortwave infrared fluorescence imaging with the clinically approved near-infrared dye indocyanine green

Significance Imaging in the shortwave IR (SWIR) spectral window allows the observation of processes deep within living animals. Recent studies have shown that SWIR imaging enables unprecedented imaging opportunities, including contact-free monitoring of vital signs, generation of microvasculature blood flow maps, real-time metabolic imaging, and molecularly targeted imaging. Yet, whereas bright SWIR fluorophores have been developed for preclinical research settings, applications in the clinic have been held back by the conventional belief that no clinically approved fluorophore is available. Here, we show that indocyanine green, a clinically approved near-IR dye, exhibits a remarkable amount of SWIR emission, which enables state-of-the-art SWIR imaging with direct translation potential into clinical settings, and even outperforms other commercially available SWIR emitters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Imaging with the fluorogenic dye Basic Fuchsin reveals subcellular patterning and ecotype variation of lignification in Brachypodium distachyon

Lignin is a complex polyphenolic heteropolymer that is abundant in the secondary cell walls of plants and functions in growth and defence. It is also a major barrier to the deconstruction of plant biomass for bioenergy production, but the spatiotemporal details of how lignin is deposited in actively lignifying tissues and the precise relationships between wall lignification in different cell types and developmental events, such as flowering, are incompletely understood. Here, the lignin-detecting fluorogenic dye, Basic Fuchsin, was adapted to enable comparative fluorescence-based imaging of lignin in the basal internodes of three Brachypodium distachyon ecotypes that display divergent flowering times. It was found that the extent and intensity of Basic Fuchsin fluorescence increase over time in the Bd21-3 ecotype, that Basic Fuchsin staining is more widespread and intense in 4-week-old Bd21-3 and Adi-10 basal internodes than in Bd1-1 internodes, and that Basic Fuchsin staining reveals subcellular patterns of lignin in vascular and interfascicular fibre cell walls. Basic Fuchsin fluorescence did not correlate with lignin quantification by acetyl bromide analysis, indicating that whole-plant and subcellular lignin analyses provide distinct information about the extent and patterns of lignification in B. distachyon . Finally, it was found that flowering time correlated with a transient increase in total lignin, but did not correlate strongly with the patterning of stem lignification, suggesting that additional developmental pathways might regulate secondary wall formation in grasses. As a result, this study provides a new comparative tool for imaging lignin in plants and helps inform our views of how lignification proceeds in grasses.

59 BASIC BIOLOGICAL SCIENCES↗

Enhancement of Fluorescence and Raman Scattering in Cyanine-Dye Molecules on the Surface of Silicon-Coated Silver Nanoparticles

A method of formation of a composite structure based on silver nanoparticles and a thin protective silicon film (AgNPs/Si) is developed. Enhancement of the fluorescence and Raman scattering in cyaninedye molecules deposited onto the formed nanostructure is observed. The optical properties and morphology stability of particles that are in contact with cyanine-dye solutions in organic solvents are studied. It is shown that the AgNPs/Si composite structure can be multiply used as an SERS-active surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Photolysis of Diazo Dye in Aqueous Solutions of Metal Nitrates

The photolysis of Chicago Blue Sky diazo dye is studied. It is experimentally shown that the presence of metal nitrates in aqueous solutions changes the photolysis mechanism and sharply increases the photolysis rate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Raman Scattering of Light by Molecules of Methyl Orange Dye on the Surface of Silicon Containing Ion-Synthesized Silver Nanoparticles

The possibility of using a new composite material based on porous silicon containing silver nanoparticles and synthesized by means of a unique implantation nanotechnology as an optically sensitive material in biological and chemical sensors is tested experimentally. It is demonstrated that detection of small amounts of the studied organic substance (methyl orange dye) is possible due to the effect of surface-enhanced Raman scattering (SERS) from the molecules affected by the local electromagnetic field of the silver nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Study of the deposition features of the organic dye Rhodamine B on the porous surface of silicon with different pore sizes

The deposition features of the organic dye Rhodamine B on the porous surface of silicon with average pore sizes of 50–100 and 100–250 nm are studied. Features of the composition and optical properties of the obtained systems are studied using infrared and photoluminescence spectroscopy. It is found that Rhodamine-B adsorption on the surface of por-Si with various porosities is preferentially physical. The optimal technological parameters of its deposition are determined.

36 MATERIALS SCIENCE↗

Power Conversion Efficiencies of Perovskite and Dye-Sensitized Solar Cells under Various Solar Radiation Intensities

We present the results of a comparative study on behaviour of the photovoltaic parameters in perovskite (PSC), dye-sensitized (DSC) and crystalline silicon (c-Si) solar cells under various intensities of solar radiation (10–1000 W/m{sup 2}). It was found that unlike c-Si, the power conversion efficiencies of PSC and DSC under low radiation intensities are comparable with the corresponding values observed under standard light intensity of 1000 W/m{sup 2} (AM1.5G). We have shown that high performance of the PSC and DSC at low and diffuse lighting conditions can be explained by the properties of the nanostructured TiO{sub 2}-based photoelectrodes depending on the structure, morphology and the thickness of the TiO{sub 2} layers.

14 SOLAR ENERGY↗

Fabrication and Characterization of Front-Illuminated Dye-Sensitized Solar Cells with Anodic Titanium Oxide Nanotubes

We have fabricated front-side illuminated dye-sensitized solar cells (DSSCs) with a thin film of vertically oriented TiO2 nanotubes used as the negative electrode. The TiO2 nanotube film was formed by anodizing a metallic titanium thin film that was deposited on a transparent conductive oxide (TCO) layer with an intermediate, protective TiO2 layer.We characterized the structural and electronic properties of the formed TiO2 nanotube films. Titanium tetrachloride (TiCl4) treatment was applied on the TiO2 nanotube film to improve the performance of the DSSCs. We have investigated effects of TiCl4 treatment on the solar cell parameters of the DSSCs: short-circuit current density (ISC), open-circuit voltage (Voc), ideal factor (n), series resistance (Rs) and shunt resistance (Rsh). The parameters have been derived by analyzing measured I-V characteristic of the DSSCs on the basis of the method we have previously proposed. We demonstrate that the performance of the DSSCs is improved by TiCl4 treatment. We discuss the effects of TiCl4 treatment on the performance on the basis of the derived cell parameters.

Kojima, Ryota↗

Enhancing Charge Injection in Polyoxometalate-based Dye-Sensitized Solar Cells

A series of 3d-transition metal containing polyoxometalates have been synthesized. These materials were successfully characterized using a variety of spectroscopic and electrochemical techniques. A selected polyoxometalate was sensitized with a porphyrin-based dye to permit for more efficient solar spectrum utilization.

14 SOLAR ENERGY↗

Biomimetic Light Harvesting Complexes Based on Self-Assembled Dye-DNA Nanostructures (Final Technical Report)

A fundamental limitation in the development of artificial molecular light harvesting structures is that generally if one places pigment molecules close enough to achieve very high energy transfer efficiency and absorbance cross section, the dyes interact in such a way that self-quenching occurs. This limits both the optical cross section and the overall efficiency of light capture in such systems. Nature overcomes this problem and achieves efficient energy transfer without self-quenching by controlling the environment, vibration characteristics, orientation and dynamics of the pigments involved in light harvesting. Natural light harvesting systems have evolved highly intricate chromophore architectures of protein-bound organic molecules that absorb and funnel solar energy with high efficiency and fast transfer rates using elegant excitonic circuitries. Nature achieves this precise control over the properties of pigment complexes by using specific proteins as templates to guide the formation of very well-defined pigment aggregates, groups of pigment molecules that are in close enough contact to undergo excitonic interactions resulting in new electronic properties that were not present in the monomer. In synthetic systems, pigment aggregates are well known, and J-aggregates and H-aggregates have been long studied for their unique properties. In Nature, the chlorosomes of green bacteria form what appear to be classical J-aggregates and the light harvesting complexes of purple nonsulfur bacteria form ring structures that have many of the properties of J-aggregates such as a red-shifted absorbance spectrum and excited states that are delocalized over multiple pigment molecules. These photosynthetic systems leverage the spectral and enhanced transport properties of J-like aggregates to achieve fast exciton transport within the antenna and thus high light-harvesting efficiency. The close interaction of the pigments results in substantial electronic coupling that lifts the degeneracy of excitonic states and therefore modifies the absorption and emission spectra of the monomer. In the case of J-aggregation, lower energy excitonic states acquire significant oscillator strength, resulting in a characteristic bathochromic shift of the absorption and fluorescence and often superradiant delocalized exciton states.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Piezocatalytic ZnS:Mn 2+ Nanocrystals for Enhanced Organic Dye Degradation

Piezocatalysis, an emerging approach that harnesses mechanical energy to drive chemical reactions, has garnered significant attention due to its potential applications in diverse fields, particularly in environmental remediation. Its broader application, however, is often hindered by the low efficiency of existing piezocatalytic materials. Here, we report the synthesis of Mn 2+ -doped ZnS nanocrystals with improved piezoelectric properties using an emulsion-based colloidal assembly technique. Through well-controlled Mn 2+ doping, these nanocrystals demonstrate high piezocatalytic activity for degrading organic dyes under ultrasonic vibration. The optimal performance is achieved with 3% Mn 2+ doping, outperforming many existing piezocatalysts. Mechanistic studies reveal the generation of reactive oxygen species as the primary driving force for degradation. Notably, pre-excitation with UV light further boosts the piezocatalytic efficiency of these metal ion-doped ZnS nanocrystals by filling electron trap states, leading to improved overall performance. This research paves the way for developing high-performance piezocatalysts, expanding the potential of piezocatalysis for a wide range of applications.

36 MATERIALS SCIENCE↗