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RSC Advances Apr 2024The benzothiophene based chromophores (A1D1-A1D5) with A-π-A configuration were designed end-capped tailoring with benzothiophene type acceptors using reference...
The benzothiophene based chromophores (A1D1-A1D5) with A-π-A configuration were designed end-capped tailoring with benzothiophene type acceptors using reference compound (A1R). Quantum chemical calculations were accomplished at M06/6-311G(d,p) level to probe optoelectronic and photophysical properties of designed chromophores. Therefore, frontier molecular orbitals (FMOs), binding energy (), open circuit voltage (), transition density matrix (TDM), density of state (DOS) and UV-Vis analyses of A1R and A1D1-A1D5 were accomplished. The designed compounds (A1D1-A1D5) exhibited absorption values in the visible region as 616.316-649.676 nm and 639.753-665.508 nm in gas and chloroform phase, respectively, comparing with reference chromophore. An efficient charge transference from HOMO towards LUMO was found in A1D1-A1D5 chromophores which was further supported by TDM and DOS analyses. Among all chromophores, A1D2 exhibited unique characteristics such as reduced band gap (2.354 eV), higher softness ( = 0.424 eV), lower exciton binding energy (0.491 eV) and maximum value of open circuit voltage ( = 1.981 V). Consequently, A1D2 may be considered as potential candidate for the development of optoelectronic devices. These analyses revealed that the studied compounds exhibited promising findings. They may be utilized in the realm of organic solar cells.
PubMed: 38645518
DOI: 10.1039/d3ra06817j -
Biomedical Optics Express Apr 2024The clinical management of coronary artery disease and the prevention of acute coronary syndromes require knowledge of the underlying atherosclerotic plaque...
The clinical management of coronary artery disease and the prevention of acute coronary syndromes require knowledge of the underlying atherosclerotic plaque pathobiology. Hybrid imaging modalities capable of comprehensive assessment of biochemical and morphological plaques features can address this need. Here we report the first implementation of an intravascular catheter system combining fluorescence lifetime imaging (FLIm) with polarization-sensitive optical coherence tomography (PSOCT). This system provides multi-scale assessment of plaque structure and composition via high spatial resolution morphology from OCT, polarimetry-derived tissue microstructure, and biochemical composition from FLIm, without requiring any molecular contrast agent. This result was achieved with a low profile (2.7 Fr) double-clad fiber (DCF) catheter and high speed (100 fps B-scan rate, 40 mm/s pullback speed) console. Use of a DCF and broadband rotary junction required extensive optimization to mitigate the reduction in OCT performance originating from additional reflections and multipath artifacts. This challenge was addressed by the development of a broad-band (UV-visible-IR), high return loss (47 dB) rotary junction. We demonstrate in phantoms, swine coronary specimens and swine heart (percutaneous coronary access) that the FLIm-PSOCT catheter system can simultaneously acquire co-registered FLIm data over four distinct spectral bands (380/20 nm, 400/20 nm, 452/45 nm, 540/45 nm) and PSOCT backscattered intensity, birefringence, and depolarization. The unique ability to collect complementary information from tissue (e.g., morphology, extracellular matrix composition, inflammation) with a device suitable for percutaneous coronary intervention offers new opportunities for cardiovascular research and clinical diagnosis.
PubMed: 38633060
DOI: 10.1364/BOE.516515 -
Sensors (Basel, Switzerland) Mar 2024In satellite remote sensing (SRS), there is a demand for large-power microwave components. A Butler matrix is essential to a transmitting antenna array in SRS. This...
In satellite remote sensing (SRS), there is a demand for large-power microwave components. A Butler matrix is essential to a transmitting antenna array in SRS. This article illustrates the electrical and mechanical design, simulation, and test results of a large-power planar beamforming network for SRS at C-band. It is a 4 × 4 Butler matrix based on square coaxial lines. Short-ended stubs are used in the Butler matrix to broaden its bandwidth by 10%, support inner conductors, and enhance heat transfer in vacuum environments. The simulation results are consistent with the measured results. The reflection coefficient is less than -18 dB, and the isolation is more than 23 dB from 3.8 GHz to 4.2 GHz. The insertion losses are less than 0.6 dB, and the phase errors are better than ±6°. The measured peak microwave power of the proposed Butler matrix is 9 kW. Its size is 440 × 400 × 40 mm. The proposed Butler matrix beamforming network can be applied to SRS systems.
PubMed: 38610343
DOI: 10.3390/s24072132 -
Colloids and Surfaces. B, Biointerfaces Jun 2024Increased glycine concentrations are associated with altered metabolism of cancer cells and is reflected in the bodily fluids of the brain cancer patients. Various...
Increased glycine concentrations are associated with altered metabolism of cancer cells and is reflected in the bodily fluids of the brain cancer patients. Various studies have been conducted in past to detect glycine as an imaging biomarker via NMR Spectroscopy tools. However, the use is limited because of the low concentration and different in vivo detection due to overlapping of peaks with myo-inositol in same spectral position. Alongside, little is known about the electrochemical potential of Glycine as a biomarker for brain cancer. The prime impetus of this study was to check the feasibility of glycine as non-invasive biomarker for brain cancer. A divergent approach to detect glycine "non-enzymatically" via unique chitosan lecithin nanocomposite has been utilised during this study. The electrochemical inactivity at provided potential that prevented glycine to get oxidized or reduced without mediator was compensated utilising the chitosan-lecithin nanocomposite. Thus, a redox mediator (Prussian blue) was used for high sensitivity and indirect detection of glycine. The chitosan nanoparticles-lecithin nanocomposite is used as a matrix. The electrochemical analysis of the onco-metabolomic biomarker (glycine) utilizing cyclic voltammetry in glycine spiked multi-Purpose artificial urine was performed to check distribution of glycine over physiological range of glycine. A wide linear range of response varying over the physiological range from 7 to 240 μM with a LOD 8.5 μM was obtained, showing potential of detection in biological samples. We have further evaluated our results via simulating the interaction of mediator and matrix with Glycine by HOMO-LUMO band fluctuations.
Topics: Glycine; Chitosan; Nanocomposites; Biosensing Techniques; Electrochemical Techniques; Humans; Lecithins; Particle Size
PubMed: 38608466
DOI: 10.1016/j.colsurfb.2024.113901 -
Nanomaterials (Basel, Switzerland) Mar 2024Efficient solar thermal conversion is crucial for renewable clean energy technologies such as solar thermal power generation, solar thermophotovoltaic and seawater...
Efficient solar thermal conversion is crucial for renewable clean energy technologies such as solar thermal power generation, solar thermophotovoltaic and seawater desalination. To maximize solar energy conversion efficiency, a solar selective absorber with tailored absorption properties designed for solar applications is indispensable. In this study, we propose a broadband selective absorber based on amorphous carbon (a-C) metamaterials that achieves high absorption in the ultraviolet (UV), visible (Vis) and near-infrared (NIR) spectral ranges. Additionally, through metal doping, the optical properties of carbon matrix materials can be modulated. We introduce Ti@a-C thin film into the nanostructure to enhance light absorption across most of the solar spectrum, particularly in the NIR wavelength band, which is essential for improving energy utilization. The impressive solar absorptivity and photothermal conversion efficiency reach 97.8% and 95.6%, respectively. Notably, these superior performances are well-maintained even at large incident angles with different polarized states. These findings open new avenues for the application of a-C matrix materials, especially in fields related to solar energy harvesting.
PubMed: 38607115
DOI: 10.3390/nano14070580 -
Nature May 2024Compared to polycrystalline semiconductors, amorphous semiconductors offer inherent cost-effective, simple and uniform manufacturing. Traditional amorphous hydrogenated...
Compared to polycrystalline semiconductors, amorphous semiconductors offer inherent cost-effective, simple and uniform manufacturing. Traditional amorphous hydrogenated Si falls short in electrical properties, necessitating the exploration of new materials. The creation of high-mobility amorphous n-type metal oxides, such as a-InGaZnO (ref. ), and their integration into thin-film transistors (TFTs) have propelled advancements in modern large-area electronics and new-generation displays. However, finding comparable p-type counterparts poses notable challenges, impeding the progress of complementary metal-oxide-semiconductor technology and integrated circuits. Here we introduce a pioneering design strategy for amorphous p-type semiconductors, incorporating high-mobility tellurium within an amorphous tellurium suboxide matrix, and demonstrate its use in high-performance, stable p-channel TFTs and complementary circuits. Theoretical analysis unveils a delocalized valence band from tellurium 5p bands with shallow acceptor states, enabling excess hole doping and transport. Selenium alloying suppresses hole concentrations and facilitates the p-orbital connectivity, realizing high-performance p-channel TFTs with an average field-effect hole mobility of around 15 cm V s and on/off current ratios of 10-10, along with wafer-scale uniformity and long-term stabilities under bias stress and ambient ageing. This study represents a crucial stride towards establishing commercially viable amorphous p-channel TFT technology and complementary electronics in a low-cost and industry-compatible manner.
PubMed: 38599238
DOI: 10.1038/s41586-024-07360-w -
Nature Communications Apr 2024Creating circularly polarized organic afterglow system with elevated triplet energy levels, suppressed non-radiative transitions, and effective chirality, which are...
Creating circularly polarized organic afterglow system with elevated triplet energy levels, suppressed non-radiative transitions, and effective chirality, which are three critical prerequisites for achieving blue circularly polarized afterglow, has posed a formidable challenge. Herein, a straightforward approach is unveiled to attain blue circularly polarized afterglow materials by covalently self-confining isolated chiral chromophore within polymer matrix. The formation of robust hydrogen bonds within the polymer matrix confers a distinctly isolated and stabilized molecular state of chiral chromophores, endowing a blue emission band at 414 nm, lifetime of 3.0 s, and luminescent dissymmetry factor of ~ 10. Utilizing the synergistic afterglow and chirality energy transfer, full-color circularly polarized afterglow systems are endowed by doping colorful fluorescent molecules into designed blue polymers, empowering versatile applications. This work paves the way for the streamlined design of blue circularly polarized afterglow materials, expanding the horizons of circularly polarized afterglow materials into various domains.
PubMed: 38594234
DOI: 10.1038/s41467-024-47240-5 -
Journal of Colloid and Interface Science Jul 2024Ultraviolet B (UVB) radiation can compromise the functionality of the skin barrier through various mechanisms. We hypothesize that UVB induce photochemical alterations...
AIM
Ultraviolet B (UVB) radiation can compromise the functionality of the skin barrier through various mechanisms. We hypothesize that UVB induce photochemical alterations in the components of the outermost layer of the skin, known as the stratum corneum (SC), and modulate its antioxidative defense mechanisms. Catalase is a well-known antioxidative enzyme found in the SC where it acts to scavenge reactive oxygen species. However, a detailed characterization of acute UVB exposure on the activity of native catalase in the SC is lacking. Moreover, the effects of UVB irradiation on the molecular dynamics and organization of the SC keratin and lipid components remain unclear. Thus, the aim of this work is to characterize consequences of UVB exposure on the structural and antioxidative properties of catalase, as well as on the molecular and global properties of the SC matrix surrounding the enzyme.
EXPERIMENTS
The effect of UVB irradiation on the catalase function is investigated by chronoamperometry with a skin covered oxygen electrode, which probes the activity of native catalase in the SC matrix. Circular dichroism is used to explore changes of the catalase secondary structure, and gel electrophoresis is used to detect fragmentation of the enzyme following the UVB exposure. UVB induced alterations of the SC molecular dynamics and structural features of the SC barrier, as well as its water sorption behavior, are investigated by a complementary set of techniques, including natural abundance C polarization transfer solid-state NMR, wide-angle X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and dynamic vapor sorption microbalance.
FINDINGS
The findings show that UVB exposure impairs the antioxidative function of catalase by deactivating both native catalase in the SC matrix and lyophilized catalase. However, UVB radiation does not alter the secondary structure of the catalase nor induce any observable enzyme fragmentation, which otherwise could explain deactivation of its function. NMR measurements on SC samples show a subtle increase in the molecular mobility of the terminal segments of the SC lipids, accompanied by a decrease in the mobility of lipid chain trans-gauche conformers after high doses of UVB exposure. At the same time, the NMR data suggest increased rigidity of the polypeptide backbone of the keratin filaments, while the molecular mobility of amino acid residues in random coil domains of keratin remain unaffected by UVB irradiation. The FTIR data show a consistent decrease in absorbance associated with lipid bond vibrations, relative to the main protein bands. Collectively, the NMR and FTIR data suggest a small modification in the composition of fluid and solid phases of the SC lipid and protein components after UVB exposure, unrelated to the hydration capacity of the SC tissue. To conclude, UVB deactivation of catalase is anticipated to elevate oxidative stress of the SC, which, when coupled with subtle changes in the molecular characteristics of the SC, may compromise the overall skin health and elevate the likelihood of developing skin disorders.
Topics: Catalase; Ultraviolet Rays; Humans; Epidermis; Skin; Keratins
PubMed: 38593652
DOI: 10.1016/j.jcis.2024.03.200 -
Spectrochimica Acta. Part A, Molecular... Jul 2024High spectral power density provided by advances in external cavity quantum cascade lasers (EC-QCL) have enabled increased transmission path lengths in mid-infrared...
Multivariate curve resolution -alternating least squares augmented with partial least squares baseline correction applied to mid-IR laser spectra resolves protein denaturation by reducing rotational ambiguity.
High spectral power density provided by advances in external cavity quantum cascade lasers (EC-QCL) have enabled increased transmission path lengths in mid-infrared (mid-IR) spectroscopy for more sensitive measurement of proteins in aqueous solutions. These extended path lengths also facilitate flow through measurements by avoiding congestion of the flow cell by protein aggregates. Despite the advantages presented by laser-based mid-IR spectroscopy of proteins, extraction of secondary structure information from spectra, especially in the presence of complex multi-component matrices with overlapping spectral features, remains an impediment that requires fine tuning of evaluation algorithms (e.g., band fitting, interpretation of second derivative spectra etc.). In this work, the use of multivariate curve resolution alternating least squares (MCR-ALS) for the analysis of a chemical de- and renaturation experiment has been demonstrated, since this technique offers the second-order advantage of extracting spectral signatures and concentration profiles even in the presence of unknown, uncalibrated constituents. Furthermore, we exhibit a partial least squares regression (PLSR) based subtraction of matrix component spectra prior to MCR-ALS as a method to obtain secondary structure information even in the absence of reference spectra. These approaches are showcased using the online reaction monitoring of the titration of β-lactoglobulin (β-LG) in water against the surfactants sodium dodecyl sulfate (SDS) and octaethylene glyol monododecyl ether (C12E8), using a commercially available laser-based IR spectrometer. Results for the automated PLSR correction plus MCR-ALS approach compare favorably to an MCR-ALS standalone approach using initial estimates as well as analysis of secondary structure using data processed with a manual baseline correction. The herein described chemometric approach suggests a way to simplify the challenge of handling complex matrices in protein structure analysis by isolating the background from the protein contributions, prior to analysis via other soft-modelling techniques. Consequently, the findings of this study indicate the suitability of online reaction monitoring through mid-IR spectroscopy combined with chemometric techniques as a potential tool in downstream quality control and process automation.
PubMed: 38593537
DOI: 10.1016/j.saa.2024.124228 -
ACS Applied Materials & Interfaces Apr 2024In this study, we examine the surface-derived electronic and chemical structures of nanostructured GaRh alloys as a model system for supported catalytically active...
In this study, we examine the surface-derived electronic and chemical structures of nanostructured GaRh alloys as a model system for supported catalytically active liquid metal solutions (SCALMS), a novel catalyst candidate for dehydrogenation reactions that are important for the petrochemical and hydrogen energy industry. It is reported that under ambient conditions, SCALMS tends to form a gallium oxide shell, which can be removed by an activation treatment at elevated temperatures and hydrogen flow to enhance the catalytic reactivity. We prepared a 7 at. % Rh containing the GaRh sample and interrogated the evolution of the surface chemical and electronic structure by photoelectron spectroscopy (complemented by scanning electron microscopy) upon performing surface oxidation and (activation treatment mimicking) annealing treatments in ultrahigh vacuum conditions. The initially pronounced Rh 4d and Fermi level-derived states in the valence band spectra disappear upon oxidation (due to formation of a GaO shell) but reemerge upon annealing, especially for temperatures of 600 °C and above, i.e., when the GaO shell is efficiently being removed and the Ga matrix is expected to be liquid. At the same temperature, new spectroscopic features at both the high and low binding energy sides of the Rh 3d spectra are observed, which we attribute to new GaRh species with depleted and enriched Rh contents, respectively. A liquefied and GaO-free surface is also expected for GaRh SCALMS at reaction conditions, and thus the revealed high-temperature properties of the GaRh alloy provide insights about respective catalysts at work.
PubMed: 38591845
DOI: 10.1021/acsami.4c02286