Systematic investigation on the rational design and optimization of bi-based metal oxide semiconductors in photocatalytic applications.

To address the global energy shortage and mitigate greenhouse gas emissions on a massive scale, it is critical to explore novel and efficient photocatalysts for the utilization of renewable resources. Bi-based metal oxide (BixMOy) semiconductors composed of bismuth, transition metal, and oxygen atoms have demonstrated improved photocatalytic activity and product selectivity. The vast number of element combinations available for BixMOymaterials provides a huge compositional space for the rational design and isolation of promising photocatalysts for specific applications. In this study, we have systematically investigated the electronic and optical properties over Bi2O3and a series of selected BixMOygroup materials (BiVO4, BiFeO3, BiCoO3, and BiCrO3) by calculating band structure, basic optical property features, mobility and separation of charge carriers. It is clearly noted that the band gap and band edge position of the BixMOygroup materials can be tuned in a wide range in comparison to Bi2O3. Similarly, the light response of BixMOyalso can be broadened from the ultraviolet to the visible light region by adjusting the selection of transition metals. Additionally, the analysis of the effective mass of charge carriers of these materials further confirms their possibility in photocatalytic reaction applications because of the appropriate separation efficiency and mobility of carriers. A selection of experimental investigations on the crystal structure, composition, and optical properties of Bi2O3, BiVO4, and BiFeO3as well as their catalytic performance in the degradation of methylene blue over was also conducted, which agree well with the theoretical predictions.

Quantitative skin surface hydration measurement by visible optical image processing: A pilot study.

BACKGROUND: Skin barrier function is significantly impacted by skin moisture. Most non-invasive evaluation techniques to measure skin surface hydration relying on its electrical properties, which are limited in scope and have unstable operations. Applying image processing for skin hydration assessment is uncommon, with an emphasis on skin-capacitive pictures and near-infrared images in general, which demand a certain spectrum. As a result, there is an increasing need for wide-area skin hydration evaluation and mapping. OBJECTIVE: The study aims to propose a quantitative evaluation algorithm for skin surface hydration from visible-light images. MATERIALS AND METHODS: Three devices were applied to measure skin hydration: skin image capture device and two recognized commercial skin devices. A digital image processing system creates a new index, called GVR, to symbolize skin surface moisture. The CLAHE algorithm was applied to enhance the contrast of skin image, and after calculating it with the monochrome image, the skin reflectance image was segmented. The GVR was estimated using the values of the individual sites and the entire skin. The correlation coefficient between the three methods was examined using statistical analysis to assess the performance of GVR. RESULTS: Skin hydration estimated from visible-light images is influenced by the entire facial structure in addition to specific areas. The electrical and visible image evaluations showed a strong association with a significant difference. CONCLUSION: It was discovered that reflecting measures from visible images provide a quick and efficient way to quantify the moisture of the skin's surface.

A building-block database of distributed polarizabilities and dipole moments to estimate optical properties of biomacromolecules in isolation or in an explicitly solvated medium.

Since atomic or functional-group properties in the bulk are generally not available from experimental methods, computational approaches based on partitioning schemes have emerged as a rapid yet accurate pathway to estimate the materials behavior from chemically meaningful building blocks. Among several applications, a comprehensive and systematically built database of atomic or group polarizabilities and related opto-electronic quantities would be very useful not only to envisage linear or non-linear optical properties of biomacromolecules but also to improve the accuracy of classical force fields devoted to simulate biochemical processes. In this work, we propose the first entries of such database that contains distributed polarizabilities and dipole moments extracted from fragments of peptides. Twenty three prototypical conformers of the dipeptides alanine-alanine and glycine-glycine were used to extract functional groups such as CH2 , CHCH3 , NH2 , COOH, CONH, thus allowing construction of a diversity of chemically relevant environments. To evaluate the accuracy of our database, reconstructed properties of larger peptides containing up to six residues of alanine and glycine were tested against density functional theory calculations at the M06-HF/aug-cc-pVDZ level of theory. The procedure is particularly accurate for the diagonal components of the polarizability tensor with errors up to 15%. In order to include solvent effects explicitly, the peptides were also surrounded by a box of water molecules whose distribution was optimized using the CHARMM force field. Solvent effects introduced by a classical dipole-dipole interaction model were compared to those obtained from polarizable-continuum model calculations.

Tunable Radiative Cooling by Mechanochromic Electrospun Micro-Nanofiber Matrix.

Radiative thermoregulation has been regarded as an energy-efficient method for thermal management. In this study, the development of a mechanoresponsive polydimethylsiloxane (PDMS) micro-nanofiber matrix capable of both sub-ambient radiative cooling and solar heating is presented, achieved through a core-shell electrospinning technique. The electrospun PDMS micro-nanofibers, with diameters comparable to the solar wavelengths, exhibit excellent solar reflectivity (≈93%) while preserving its pristine high infrared (IR) emissivity. As a result, the electrospun PDMS radiative cooler (EPRC) successfully demonstrated sub-ambient radiative cooling performance (≈3.8°C) during the daytime. Furthermore, the exceptional resilient property of PDMS facilitated the reversible alteration of the structural morphology created by the fiber-based matrix under mechanical force, resulting in the modulation of solar reflectivity (≈80%). The precise modulation of solar reflectivity enabled reversibly switchable multi-step radiative thermoregulation, offering enhanced flexibility in addressing varying thermal environments even in maintaining the desired temperature. The findings of this work offer a promising approach toward dynamic radiative thermoregulation, which holds significant potential for addressing global climate change concerns and energy shortage.

Xanthene-Separated 24 π-Electron Antiaromatic Rosarin Dimer.

Antiaromatic molecules have recently received attention because of their intrinsic properties, such as high reactivity and their narrow HOMO-LUMO gaps. Stacking of antiaromatic molecules has been predicted to induce three-dimensional aromaticity via frontier orbital interactions. Here, we report a covalently linked π-π stacked rosarin dimer that has been examined experimentally by steady-state absorption and transient absorption measurements and theoretically by quantum chemical calculations, including time-dependent density functional theory, anisotropy of induced current density, and nucleus-independent chemical shift calculations. Relative to the corresponding monomer, the dimer exhibits diminished antiaromaticity upon lowering the temperature to 77 K, a finding ascribed to intramolecular interactions between the macrocyclic rosarin subunits.

Synthesis, Photoswitching Behavior and Nonlinear Optical Properties of Substituted Tribenzo[a,d,g]coronene.

A family of tribenzocoronene derivatives bearing various substituents (3) were constructed through the Diels-Alder reaction, followed by the Scholl oxidation, where the molecular structure of 3b was determined via single crystal X-ray diffraction analysis. The effect of substitution on the optical and electrochemical property was systematically investigated, with the assistance of theoretical calculations. Moreover, the thin films of the resulting molecules 3b and 3e complexed with fullerene produced strong photocurrent response upon irradiation of white light. In addition, 3b and 3e exhibit a positive nonlinear optical response resulting from the two-photon absorption and excited state absorption processes.

Preventing the Galvanic Replacement Reaction toward Unconventional Bimetallic Core-Shell Nanostructures.

A bimetallic core-shell nanostructure is a versatile platform for achieving intriguing optical and catalytic properties. For a long time, this core-shell nanostructure has been limited to ones with noble metal cores. Otherwise, a galvanic replacement reaction easily occurs, leading to hollow nanostructures or completely disintegrated ones. In the past few years, great efforts have been devoted to preventing the galvanic replacement reaction, thus creating an unconventional class of core-shell nanostructures, each containing a less-stable-metal core and a noble metal shell. These new nanostructures have been demonstrated to show unique optical and catalytic properties. In this work, we first briefly summarize the strategies for synthesizing this type of unconventional core-shell nanostructures, such as the delicately designed thermodynamic control and kinetic control methods. Then, we discuss the effects of the core-shell nanostructure on the stabilization of the core nanocrystals and the emerging optical and catalytic properties. The use of the nanostructure for creating hollow/porous nanostructures is also discussed. At the end of this review, we discuss the remaining challenges associated with this unique core-shell nanostructure and provide our perspectives on the future development of the field.

Iridium-Catalyzed Synthesis of Chiral 1,2,3-Triazoles Units and Precise Construction of Stereocontrolled Oligomers.

Iridium-catalyzed azide-thioalkyne cycloaddition reaction (IrAAC) has proved to be a powerful tool for the synthesis of fully substituted 1,2,3-triazole compounds with exclusive regioselectivity. Here we report its successful use in the precise construction of stereocontrolled oligomers that have great potential in diverse applications. Starting with the azide derived from L-prolinol and different functionalized thioalkynes, chiral 1,2,3-triazole units were fabricated with high efficiency under the IrAAC condition, which were further assembled into stereocontrolled oligotriazoles through metal-free exponential growth strategies. The structure and uniformity of these oligomers were well identified by 1H NMR, size-exclusion chromatography, and mass spectrometry, the stereoregularity of which were studied through circular dichroism and circular polarized luminescence analysis.

Inhomogeneous linear responses and transport in armchair graphene nanoribbons in the presence of elastic scattering.

Within linear-response theory we derive a response function that thoroughly accounts for the influence of elastic scattering and is valid beyond the long-wavelength limit. We use the theory to evaluate the polarization function and the conductivity in metallic armchair graphene nanoribbons in the Lindhard approximation for intra-band and inter-band transitions and for a relaxation timeτthat is not constant. We obtain a logarithmic behaviour in the scattering-independent polarization function not only for intra-band transitions, as is usually the case for one-dimensional systems, but also for inter-band transitions. Modifying the screening wave vector and the impurity density in the long-wavelength limit strongly influences the relaxation time. In contrast, for large wave vectors, this modification leads to a conservative value ofτ. We show that the imaginary part of the impurity-dependent conductivity varies with the wave vector while its scattering-independent part exists only for a single value of the wave vector.

Spectroscopic Behavior and Photophysical Parameters of 2-(Acetoxymethyl)-6-(1,2,4-triazinylaminodihydroquinazolinyl)tetrahydropyran Derivative in Different Solid Hosts.

Optical and photophysical properties of 6-substituted-1,2,4-Triazine fluorescent derivative dye doped in silicate based sol-gel, homopolymer of methyl methacrylate (PMMA), and copolymer (MMA/diethylene glycol dimethacrylate) (DEGDMA) were investigated. The pores of different hosts and caging of the dye were found to effect on the parameters such as molar absorptivity, cross sections of singlet-singlet electronic absorption and emission spectra, excited state lifetime, quantum yield of fluorescence. The dipole moment of electronic transition, the length of attenuation and oscillator strength of electronic transition from So → S1 have been calculated. The dye was pumped with different powers using 3rd harmonic Nd: YAG laser of 355 nm and pulse duration 8 ns, with repetition rate 10 Hz. Good photo stability for dye was attained. After 55,000 pumping pulses of (10 mJ/pulse), the photo-stabilities were decreased to 53%, 48%, and 45% of the initial ASE of dye in sol gel, PMMA, and Co-polymer respectively. The dye in sol-gel matrix showed improvement of photo stability compared with those in organic polymeric matrices.

Halide Perovskite Semiconductor Lasers: Materials, Cavity Design, and Low Threshold.

Solution-processable semiconductor lasers have been a long-standing challenge for next-generation displays, light sources, and communication technologies. Metal halide perovskites, which combine the advantages of inorganic and organic semiconductors, have recently emerged not only as excellent candidates for solution-processable lasers but also as potential complementary gain materials for filling the "green gap" and supplement industrial nanolasers based on classic II-VI/III-V semiconductors. Numerous perovskite lasers have been developed successfully with superior performance in terms of cost-effectiveness, low threshold, high coherence, and multicolor tunability. This mini review surveys the development, current status, and perspectives of perovskite lasers, categorized into thin film lasers, nanocrystals lasers, microlasers, and device concepts including polariton and bound-in-continuum lasers with a focus on material fundamentals, cavity design, and low-threshold devices in addition to critical issues such as mass fabrication and applications.

Innovative Green Chemistry Approach to Synthesis of Sn2+-Metal Complex and Design of Polymer Composites with Small Optical Band Gaps.

In this work, the green method was used to synthesize Sn2+-metal complex by polyphenols (PPHs) of black tea (BT). The formation of Sn2+-PPHs metal complex was confirmed through UV-Vis and FTIR methods. The FTIR method shows that BT contains NH and OH functional groups, conjugated double bonds, and PPHs which are important to create the Sn2+-metal complexes. The synthesized Sn2+-PPHs metal complex was used successfully to decrease the optical energy band gap of PVA polymer. XRD method showed that the amorphous phase increased with increasing the metal complexes. The FTIR and XRD analysis show the complex formation between Sn2+-PPHs metal complex and PVA polymer. The enhancement in the optical properties of PVA was evidenced via UV-visible spectroscopy method. When Sn2+-PPHs metal complex was loaded to PVA, the refractive index and dielectric constant were improved. In addition, the absorption edge was also decreased to lower photon. The optical energy band gap decreases from 6.4 to 1.8 eV for PVAloaded with 30% (v/v) Sn2+-PPHs metal complex. The variations of dielectric constant versus wavelength of photon are examined to measure localized charge density (N/m*) and high frequency dielectric constant. By increasing Sn2+-PPHs metal complex, the N/m* are improved from 3.65 × 1055 to 13.38 × 1055 m-3 Kg-1. The oscillator dispersion energy (Ed) and average oscillator energy (Eo) are measured. The electronic transition natures in composite films are determined based on the Tauc's method, whereas close examinations of the dielectric loss parameter are also held to measure the energy band gap.

Effect of NOx and RH on the secondary organic aerosol formation from toluene photooxidation.

The secondary organic aerosol (SOA) formation mechanism and physicochemical properties can highly be influenced by relative humidity (RH) and NOx concentration. In this study, we performed a laboratory investigation of the SOA formation from toluene/OH photooxidation system in the presence or absence of NOx in dry and wet conditions. The chemical composition of toluene-derived SOA was measured using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). It was found that the mass concentration of toluene decreased with increasing RH and NOx concentration. However, the change of SOA chemistry composition (f44, O/C) with increased RH was not consistent in the condition with or without NOx. The light absorption and mass absorption coefficient (MAC) of the toluene-derived SOA only increased with RH in the presence of NOx. In contrast, MAC is invariant with RH in the absence of NOx. HR-ToF-AMS results showed that, in the presence of NOx, the increased nitro-aromatic compounds and N/C ratio concurrently caused the increase of SOA light absorption and O/C in wet conditions, respectively. The relative intensity of CHON and CHOxN family to the total nitrogen-containing organic compounds (NOCs) increased with the increasing RH, and be the major components of NOCs in wet condition. This work revealed a synergy effect of NOx and RH on SOA formation from toluene photooxidation.

A Hybrid Antiperovskite with Strong Linear and Second-Order Nonlinear Optical Responses.

Antiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second-order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs3 Cl(HC3 N3 S3 ) (I), which features a quasi-one-dimensional antiperovskite structure composed of ClCs6 polyhedra and A-site [HC3 N3 S3 ]2- rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH2 PO4 and exceptionally large birefringence of 0.52. The first-principles calculations and structural analyses reveal that [HC3 N3 S3 ]2- is the "material gene" while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second-order nonlinear optical responses.

Pseudospectral implementations of long-range corrected density functional theory.

We have implemented pseudospectral density-functional theory (DFT) with long-range corrected DFT functionals (PS-LRC) in quantum mechanics package Jaguar, and applied it in the calculations of geometry optimizations, dimmer interaction energies, polarizabilities and first-order hyperpolarizabilities, harmonic vibrational frequencies, S1 and T1 excitation energies, singlet-triplet gaps, charge transfer numbers, oscillator strengths, reaction barrier heights, electron-transfer couplings, and charge-transfer excitation energies. From our accuracy benchmark analysis, PS grids, PS dealiasing functions, PS atomic corrections, PS multigrid strategy, PS length scales, and PS cutoff scheme perform well in PS DFT with LRC density functionals with very small and ignorable deviations when compared to the conventional spectral (CS) method. The timing benchmark study of S1 excitation energy calculations of fullerenes (Cn , n up to 540) demonstrates that PS-LRC achieves 1.4-8.4-fold speedups in SCF, 22-32-fold speedups in Tamm-Dancoff approximation, and 6-15-fold speedups in total wall clock time with an average error 0.004 eV of excitation energies compared to the CS method.

Catalyst-assisted heteroepitaxial strategy for highly orderedß-Ga2O3nanoarrays and their optical property investigation.

In this work, we demonstrate the growth of highly orderedß-Ga2O3nanoarrays with (001) preferred growth plane for the first time through a facile heteroepitaxial strategy using metal Ga and c-sapphire as Ga precursor and monocrystalline substrate. The (001) preferred growth plane means that theß-Ga2O3nanowires grow along the normal direction of the (001) plane. Theß-Ga2O3nanoarrays along (001) preferential plane exhibit inclined six equivalent directions that correspond to the six crystallographic symmetry of (0001)α-Al2O3. High-resolution transmission electron microscopy analyses confirm the good crystallinity and the existence of unusual epitaxial relationship of {310}ß-Ga2O3ǁ (0001)α-Al2O3and <001>ß-Ga2O3or <132>ß-Ga2O3ǁ [11¯00]α-Al2O3. UV-vis and cathodoluminescence measurements reveal the wide band gap of 4.8 eV and the strong UV-blue luminescence (300-500 nm) centered at ∼388 nm. Finally, the luminescence mechanism is further investigated with the assistance of x-ray photoelectron spectroscopy. The heteroepitaxial strategy of highly orderedß-Ga2O3nanoarrays in this work will undoubtedly pave a solid way toward the fundamental research and the applications of Ga2O3nanodevices in optoelectronic, gas sensor, photocatalyst and next-generation power electronics.

Brown Carbon in Primary and Aged Coal Combustion Emission.

Smog chamber experiments were conducted to characterize the light absorption of brown carbon (BrC) from primary and photochemically aged coal combustion emissions. Light absorption was measured by the UV-visible spectrophotometric analysis of water and methanol extracts of filter samples. The single-scattering albedo at 450 nm was 0.73 ± 0.10 for primary emissions and 0.75 ± 0.13 for aged emissions. The light absorption coefficient at 365 nm of methanol extracts was higher than that of water extracts by a factor of 10 for primary emissions and a factor of 7 for aged emissions. This suggests that the majority of BrC is water-insoluble even after aging. The mass absorption efficiency of this BrC (MAE365) for primary OA (POA) was dependent on combustion conditions, with an average of 0.84 ± 0.54 m2 g-1, which was significantly higher than that for aged OA (0.24 ± 0.18 m2 g-1). Secondary OA (SOA) dominated aged OA and the decreased MAE365 after aging indicates that SOA is less light absorbing than POA and/or that BrC is bleached (oxidized) with aging. The estimated MAE365 of SOA (0.14 ± 0.08 m2 g-1) was much lower than that of POA. A comparison of MAE365 of residential coal combustion with other anthropogenic sources suggests that residential coal combustion emissions are among the strongest absorbing BrC organics.

Investigation on the Linear and Nonlinear Properties of Morin in Presence of Reverse Micelle and Different Oil Content in Reverse Micelle.

We investigate the linear and nonlinear optical property of Morin (MN) at different concentration (1 × 10-6 and 5 × 10-6 M) within AOT reversed micelle prepared by water-in-decane microemulsion having a constant molar ratio of water-to-surfactant molecules of 40 (W = [H2O]/[AOT] = 40) as well as the function of mass fraction of nano-droplet (MFD) values of 0.01,0.04, 0.07, and 0.1 by using UV-Visible, Fluorescence, FTIR, and Z-scan techniques. The steady-state measurement indicates that the presence of microenvironment can greatly affect the tautomeric structure of morin and also Morin property in microenvironment depends upon the amount of oil and Morin concentration. The increase in dipole moment from the ground state to excited state in microenvironment indicate the change in the molecular structure on morin. Morin does not show any nonlinear absorption property but the nonlinear refractive index is observed as a function of Morin concentration as well as MFD values which are due to the thermal agitation of formed dimers. Morin nonlinearity.

Spectral Behavior and Photophysical Parameters of Dihydrophenanthro[9,10-e][1,2,4]Triazine Derivative Dyes in Sol-Gel and Methyl Methacrylate Polymer Matrices.

This paper deals with the optical and photophysical properties of dihydrophenanthro[9,10-e][1,2,4]triazine fluorescent dyes doped in Silicate based sol-gel and homo-poly methyl methacrylate (PMMA). Solid hosts were found to effect on the optical and photophysical parameters such as molar absorptivity, cross sections of singlet-singlet electronic absorption and emission spectra, excited state lifetime, quantum yield of fluorescence. The dipole moment of electronic transition, the length of attenuation and oscillator strength of electronic transition from So → S1 have been calculated. The dyes were pumped with different powers using 3rd harmonic Nd:YAG laser of 355 nm and pulse duration 8 ns, with a repetition rate at (10 Hz). Good photostability for compounds 1 and 2 were attained. It was decreased to 49% & 54% and 46% & 40% of the initial ASE of dyes in sol gel and PMMA, respectively, after 55,000 pumping pulses at (10 mJ/pulse). The dyes in sol-gel showed improved photostability compared with those in organic polymeric matrices.

Synthesis, characterization, and photoluminescence property of Nd-TUD-1.

Here, five different samples of neodymium (Nd) incorporated 3D-mesoporous siliceous materials were fabricated using a single-step hydrothermal technique. Typically, all samples were subjected to several qualitative elemental and quantitative analyses such as X-ray diffraction, N2 -adsorption/desorption, scanning electron microscopy, energy dispersive X-ray, mapping, high resolution transmission electron microscopy, diffuse reflectance ultraviolet-visible, and Raman spectroscopy. The characterization results showed that at small loading of Nd (i.e. Si/Nd < 20), only isolated centres of trivalent neodymium ions were tetrahedrally coordinated in the TUD-1 matrix. However, with increasing neodymium loading, additional nanoparticles of neodymium oxide with size 10-20 nm were embedded into silica host pores. Detailed photoluminescence (PL) analysis of all samples was carried out by recording the emission profiles at two diverse excitation wavelengths, 333 and 343 nm, to understand the effect of the Nd3+ environment on the PL emission spectra with special attention to the area between 400 and 600 nm. Most importantly, different peaks of the emission spectrum of each sample exhibited a distinct shape based on the Nd3+ environment. This performance was superior evidence that PL can be applied as a simple and efficient characterization tool to understand the nature of Nd3+ ion linkage with a silica matrix.