Active Area Research Articles

Selective fluorescent labeling of cellular proteins and its biological applications.

Proteins, which are ubiquitous in cells and critical to almost all cellular functions, are indispensable for life. Fluorescence imaging of proteins is key to understanding their functions within their native milieu, as it provides insights into protein localization, dynamics, and trafficking in living systems. Consequently, the selective labeling of target proteins with fluorophores has emerged as a highly active research area, encompassing bioorganic chemistry, chemical biology, and cell biology. Various methods for selectively labeling proteins with fluorophores in cells and tissues have been established and are continually being developed to visualize and characterize proteins. This review highlights research findings reported since 2018, with a focus on the selective labeling of cellular proteins with small organic fluorophores and their biological applications in studying protein-associated biological events. We also discuss the strengths and weaknesses of each labeling approach for their utility in living systems.

Examining the challenges of blood pressure estimation via photoplethysmogram

The use of observed wearable sensor data (e.g., photoplethysmograms [PPG]) to infer health measures (e.g., glucose level or blood pressure) is a very active area of research. Such technology can have a significant impact on health screening, chronic disease management and remote monitoring. A common approach is to collect sensor data and corresponding labels from a clinical grade device (e.g., blood pressure cuff) and train deep learning models to map one to the other. Although well intentioned, this approach often ignores a principled analysis of whether the input sensor data have enough information to predict the desired metric. We analyze the task of predicting blood pressure from PPG pulse wave analysis. Our review of the prior work reveals that many papers fall prey to data leakage and unrealistic constraints on the task and preprocessing steps. We propose a set of tools to help determine if the input signal in question (e.g., PPG) is indeed a good predictor of the desired label (e.g., blood pressure). Using our proposed tools, we found that blood pressure prediction using PPG has a high multi-valued mapping factor of 33.2% and low mutual information of 9.8%. In comparison, heart rate prediction using PPG, a well-established task, has a very low multi-valued mapping factor of 0.75% and high mutual information of 87.7%. We argue that these results provide a more realistic representation of the current progress toward the goal of wearable blood pressure measurement via PPG pulse wave analysis. For code, see our project page: https://github.com/lirus7/PPG-BP-Analysis

Efficient nitrite determination by electrochemical approach in liquid phase with ultrasonically prepared gold-nanoparticle-conjugated conducting polymer nanocomposites

An electrochemical nitrite sensor probe is introduced herein using a modified flat glassy carbon electrode (GCE) and SrTiO3 material doped with spherical-shaped gold nanoparticles (Au-NPs) and polypyrrole carbon (PPyC) at a pH of 7.0 in a phosphate buffer solution. The nanocomposites (NCs) containing Au-NPs, PPyC, and SrTiO3 were synthesized by ultrasonication, and their properties were thoroughly characterized through structural, elemental, optical, and morphological analyses with various conventional spectroscopic methods, such as field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller method. The peak currents due to nitrite oxidation were characterized in detail and analyzed using conventional cyclic voltammetry (CV) as well as differential pulse voltammetry (DPV) under ambient conditions. The sensor response increased significantly from 0.15 to 1.5 mM of nitrite ions, and the sensor was fabricated by coating a conducting agent (PEDOT:PSS) on the GCE to obtain the Au-NPs/PPyC/SrTiO3 NCs/PEDOT:PSS/GCE probe. The sensor’s sensitivity was determined as 0.5 μA/μM∙cm2 from the ratio of the slope of the linear detection range by considering the active surface area (0.0316 cm2) of the flat GCE. In addition, the limit of detection was determined as 20.00 ± 1.00 µM, which was found to be satisfactory. The sensor’s stability, pH optimization, and reliability were also evaluated in these analyses. Overall, the sensor results were found to be satisfactory. Real environmental samples were then analyzed to evaluate the sensor’s reliability through DPV, and the results showed that the proposed novel electrochemical sensor holds great promise for mitigating water contamination in the real samples with the lab-made Au-NPs/PPyC/SrTiO3 NC. Thus, this study provides valuable insights for improving sensors for broad environmental monitoring applications using the electrochemical approach.

Platinum-Ruthenium Bimetallic Nanoparticle Catalysts Synthesized Via Direct Joule Heating for Methanol Fuel Cells.

Platinum-Ruthenium (PtRu) bimetallic nanoparticles are promising catalysts for methanol oxidation reaction (MOR) required by direct methanol fuel cells. However, existing catalyst synthesis methods have difficulty controlling their composition and structures. Here, a direct Joule heating method to yield highly active and stable PtRu catalysts for MOR is shown. The optimized Joule heating condition at 1000°C over 50 microseconds produces uniform PtRu nanoparticles (6.32wt.% Pt and 2.97 wt% Ru) with an average size of 2.0 ± 0.5 nanometers supported on carbon black substrates. They have a large electrochemically active surface area (ECSA) of 239 m2 g-1 and a high ECSA normalized specific activity of 0.295mA cm-2. They demonstrate a peak mass activity of 705.9mA mgPt -1 for MOR, 2.8 times that of commercial 20 wt.% platinum/carbon catalysts, and much superior to PtRu catalysts obtained by standard hydrothermal synthesis. Theoretical calculation results indicate that the superior catalytic activity can be attributed to modified Pt sites in PtRu nanoparticles, enabling strong methanol adsorption and weak carbon monoxide binding. Further, the PtRu catalyst demonstrates excellent stability in two-electrode methanol fuel cell tests with 85.3% current density retention and minimum Pt surface oxidation after 24 h.

Coulomb Interaction-Driven Entanglement of Electrons on Helium

The generation and evolution of entanglement in many-body systems is an active area of research that spans multiple fields, from quantum information science to the simulation of quantum many-body systems encountered in condensed matter, subatomic physics, and quantum chemistry. Motivated by recent experiments exploring quantum information processing systems with electrons trapped above the surface of cryogenic noble gas substrates, we theoretically investigate the generation of entanglement between two electrons via their unscreened Coulomb interaction. The model system consists of two electrons confined in separate electrostatic traps that establish microwave-frequency quantized states of their motion. We compute the motional energy spectra of the electrons, as well as their entanglement, by diagonalizing the model Hamiltonian with respect to a single-particle Hartree product basis. We also compare our results with the predictions of an effective Hamiltonian. The computational procedure outlined here can be employed for device design and guidance of experimental implementations. In particular, the theoretical tools developed here can be used for fine-tuning and optimization of control parameters in future experiments with electrons trapped above the surface of superfluid helium or solid neon. Published by the American Physical Society 2024

Ni–P–PTFE cathode with low surface energy for enhancing electrochemical water softening performance

ABSTRACT Efficient cathode regeneration is a significant challenge in the electrochemical water softening process. This work explores the use of an electroless plating Ni–P–PTFE electrode with low surface energy for this purpose. The Ni–P–PTFE electrode demonstrates improved self-cleaning performance at high current densities. By combining the low surface energy of the electrode with fluid flushing shear force, the precipitation rate on the Ni–P–PTFE electrode remains stable at approximately 18 g/m2·h over extended periods of operation. Additionally, the cleaning efficiency of the Ni–P–PTFE electrode surpasses that of stainless steel by 66.34%. The Ni–P–PTFE electrode can maintain a larger active area and a longer operational lifespan is attributed to its self-cleaning performance derived from low surface energy. Furthermore, the loose scale layers on the electrode surface are easily removed during electrochemical water softening processes, presenting a novel approach to cathode surface design.

How Microstructures, Oxide Layers, and Charge Transfer Reactions Influence Double Layer Capacitances. Part 2: Equivalent Circuit Models

ABSTRACTIn the first part of this study, double layer (DL) capacitances of plane and porous electrodes were related to electrochemical active surface areas based on electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements. Here, these measured data are described with equivalent circuit models (ECMs), aiming to critically assess the ambiguity, reliability, and pitfalls of the parametrization of physicochemical mechanisms. For microstructures and porous electrodes, the resistive–capacitive contributions of DL in combination with resistively damped currents in pores are discussed to require the complexity of convoluted transmission line ECMs. With these ECMs, the frequency‐dependencies of the capacitances of porous electrodes are elucidated. Detailed EIS or CV data‐based reconstructions of complex microstructures are discussed as impossible due to the blending of individual structural features and the related loss of information. Microstructures in combination with charge transfer reactions and weakly conducting parts require parameter‐rich ECMs for an accurate physicochemical description of all physicochemical mechanisms contributing to the response. Nevertheless, the data of such a complex electrode in the form of an oxidized titanium electrode are fitted by an oversimplistic ECM, showing how easily unphysical parameterizations can be obtained with ECM‐based impedance analysis. In summary, trends in how microstructures, charge transfer resistances and oxide layers can influence EIS and CV data are shown, while awareness for the overinterpretation of ECM‐analysis is raised.

2D/2D Heterojunction of Cobalt‐Iron Selenide Nanolamellas/MXene for Enhanced Electrocatalytic Hydrogen Evolution

AbstractElectrochemical water splitting is considered to be a green and flexible strategy for the mass production of hydrogen fuel, while the high cost and insufficent activity of current cathode catalysts severely suffocate the widespread thriving of hydrogen economy. Herein, we present a bottom‐up assembly strategy to the controllable construction of 2D/2D heterojunctions built from cobalt‐iron selenide nanolamellas and Ti3C2Tx MXene nanosheets. This unique architectural design gives the resulting CoyFe1‐ySe2/Ti3C2Tx catalysts a series of interesting structural advantages, such as 2D/2D heterostructure, large active surface areas, modulated electronic structure, uniform CoyFe1‐ySe2 dispersion, and good electron conductivity, thereby leading to strong synergistic coupling effects. As a consequence, the optimized Co0.7Fe0.3Se2/Ti3C2Tx electrocatalyst with an appropriate Co/Fe ratio possesses unusual hydrogen evolution properties in terms of a low overpotential of 69 mV at 10 mA cm−2, a small Tafel slope of 51 mV dec−1 and reliable long‐term durability, which are more competitive than those of bare Ti3C2Tx, FeSe2 and CoSe catalysts.

Blocked Gibbs sampler for hierarchical Dirichlet processes

– Posterior computation in hierarchical Dirichlet process (HDP) mixture models is an active area of research in nonparametric Bayes inference of grouped data. Existing literature almost exclusively focuses on the Chinese restaurant franchise (CRF) analogy of the marginal distribution of the parameters, which can mix poorly and has a quadratic complexity with the sample size. A recently developed slice sampler allows for efficient blocked updates of the parameters, but is shown to be statistically unstable in our article. We develop a blocked Gibbs sampler that employs a truncated approximation of the underlying random measures to sample from the posterior distribution of HDP, which produces statistically stable results, is highly scalable with respect to sample size, and is shown to have good mixing. The heart of the construction is to endow the shared concentration parameter with an appropriately chosen gamma prior that allows us to break the dependence of the shared mixing proportions and permits independent updates of certain log-concave random variables in a block. En route, we develop an efficient rejection sampler for these random variables leveraging piece-wise tangent-line approximations. Supplementary materials, which include substantive additional details and code, are available online.

Transition Metal Mimetic π-Activation by Cationic Bismuth(III) Catalysts for Allylic C-H Functionalization of Olefins Using C═O and C═N Electrophiles.

The discovery and utilization of main-group element catalysts that behave similarly to transition metal (TM) complexes have become increasingly active areas of investigation in recent years. Here, we report a series of Lewis acidic bismuth(III) complexes that allow for the catalytic allylic C(sp3)-H functionalization of olefins via an organometallic complexation-assisted deprotonation mechanism to generate products containing new C-C bonds. This heretofore unexplored mode of main-group reactivity was applied to the regioselective functionalization of 1,4-dienes and allylbenzene substrates. Experimental and computational mechanistic studies support the key steps of the proposed catalytic cycle, including the intermediacy of elusive Bi-olefin complexes and allylbismuth species.

Photocatalytic Degradation of Carbofuran in Water Using Laser-Treated TiO2: Parameters Influence Study, Cyto- and Phytotoxicity Assessment

This study investigates the impact of changing parameters on the photocatalytic degradation of carbofuran (CBF) using laser-treated TiO2 nanotube arrays on a Ti mesh under simulated sunlight irradiation and assessing toxicity during photocatalytic degradation. Various parameters, including the stirring effect, light intensity, initial CBF concentration, and variation in the active surface area of laser-treated TiO2 photocatalysts, were examined to determine their impact on degradation efficiency. The photodegradation kinetics were monitored using ultra-performance liquid chromatography with a PDA detector (UPLC-PDA) and UV-Vis spectrophotometry, while mineralization was assessed by a total organic carbon (TOC) analyzer. The photocatalytic degradation of CBF is enhanced by an increase in the active surface area of the TiO2 photocatalyst, light intensity, and the introduction of stirring, but it decreases with an increase in the initial concentration of CBF. The toxicity assessments revealed that the cytotoxicity of CBF initially increased during the degradation process but decreased after further treatment, indicating the formation and subsequent breakdown of toxic intermediates. The phytotoxicity test showed that longer degradation times resulted in higher toxicity to plant growth. This study provides new insights into the photocatalytic degradation of CBF with TiO2, the importance of parameter optimization for more efficient treatment, and the use of toxicity tests to confirm the success of the photocatalytic process.

Eco-friendly and large-scale fabrication of NiMoN/Ni(OH)2/NF as highly efficient and stable alkaline hydrogen evolution reaction electrode

Bimetallic nickel-molybdenum nitride (NiMoN) catalysts have attracted great attention due to their remarkable similarity to group VIII noble metals in terms of electronic structure, good electron conductivity, and durability for the hydrogen evolution reaction (HER). However, the existing approaches for fabricating NiMoN catalysts usually entail a series of multiple steps and hazardous ammoniated ingredient. As a result, these methods are difficult to be scaled up for large-area fabrication towards industrial water splitting. Herein, a hierarchical composite NiMoN@Ni(OH)2@NF composite electrode with a sheet morphology was synthesized based on a rational combination of seawater etching and magnetron sputtering. This method is easily scalable for producing large-area electrodes with minimal pollution. The incorporation of Ni(OH)2@NF nanoarray carriers enhances the exposure of additional active sites on the NiMoN layer, thereby augmenting the electrochemically active specific surface area of the electrode.The as-synthesized NiMoN@Ni(OH)2@NF electrode demonstrates excellent HER activity, with an overpotential of 57 mV at 10 mA cm−2, and exhibits remarkable long-term catalytic stability for over 100 h at a current density of 100 mA cm−2.This study presents an eco-friendly and straightforward method for preparing large-scale transition metal nitride catalysts with high catalytic activity.

“Down Syndrome is Not a Curse”: parent Perspectives on the Medicalization of Down Syndrome

Background Potential clinical interventions to mitigate or eliminate symptoms of Down syndrome (DS) continue to be an active area of pre-clinical and clinical research. However, views of members of the DS community have yet to be fully explored. Methods We conducted a survey with parents/caregivers of people with DS (n = 532) to explore interest in potential therapeutic approaches during fetal development or childhood that may improve neurocognition and modulate the DS phenotype. We qualitatively analyzed open-ended responses. Results Some respondents rejected the development of therapies for DS categorically as being fundamentally ableist and promoting the erasure of diverse individuals. Many reflected tensions between the desire to improve quality of life and an aversion to erasure of a child’s personality. Conclusion Findings suggest that views on identity, personality, and disability may influence the acceptance of new interventions, especially if they are thought to mitigate positive attributes of the phenotype or negatively influence social acceptance of people with DS.

Nuclei engineering for even halide distribution in stable perovskite/silicon tandem solar cells.

Wide-bandgap (WBG) absorbers in tandem configurations suffer from poor crystallinity and weak texture, which leads to severe mixed halide-cation ion migration and phase segregation during practical operation. We control WBG film growth insensitive to compositions by nucleating the 3C phase before any formation of bromine-rich aggregates and 2H phases. The resultant WBG absorbers show improved crystallinity and strong texture with suppressed nonradiative recombination and enhanced resistance to various aging stresses. Perovskite/silicon tandem solar cells achieve power conversion efficiencies of 29.4% (28.8% assessed by a third party) in a 25-square centimeter active area and 32.5% in a 1-square centimeter active area. These solar cells retained 98.3 and 90% of the original efficiency after 1301 and 800 hours of operation at 25° and 50°C, respectively, at the maximum power point (AM 1.5G illumination, full spectrum, 1-sun) when encapsulated.

Revealing Mode Formation in Quasi-Bound States in the Continuum Metasurfaces via Near-Field Optical Microscopy.

Photonic metasurfaces offer exceptional control over light at the nanoscale, facilitating applications spanning from biosensing, and nonlinear optics to photocatalysis. Many metasurfaces, especially resonant ones, rely on periodicity for the collective mode to form, which makes them subject to the influences of finite size effects, defects, and edge effects, which have considerable negative impact at the application level. These aspects are especially important for quasi-bound state in the continuum (BIC) metasurfaces, for which the collective mode is highly sensitive to perturbations due to high-quality factors and strong near-field enhancement. Here, the mode formation in quasi-BIC metasurfaces on the individual resonator level using scattering scanning near-field optical microscopy (s-SNOM) in combination with a new image processing technique, is quantitatively investigated. It is found that the quasi-BIC mode is formed at a minimum size of 10×10-unit cells much smaller than expected from far-field measurements. Furthermore, it is shown that the coupling direction of the resonators, defects and edge states have pronounced influence on the quasi-BIC mode. This study serves as a link between the far-field and near-field responses of metasurfaces, offering crucial insights for optimizing spatial footprint and active area, holding promise for augmenting applications such as catalysis and biospectroscopy.

Mechanical Ankle Joint Axis Point on a Hip-to-Calcaneus Long Leg View Correlates Significantly With SPECT/CT Activation in Symptomatic Asymmetric Ankle Osteoarthritis.

Asymmetric joint load is the main cause of development of ankle osteoarthritis (OA). Realignment surgery aims to transfer ankle joint load from the degenerative area toward the uninvolved area. Determination of the optimal shift is still challenging. When the degenerative area is correlated to the ankle joint mechanical axis establishing an optimal target angle for corrective surgery may become more feasible. The primary aim of our study was to investigate if the area of ankle joint activation on single-photon emission computed tomography and conventional computed tomography (SPECT/CT) imaging correlates with the mechanical ankle joint axis point (MAJAP). In this cross-sectional study, patients 18 years or older with symptomatic asymmetric ankle OA and a hip-to-calcaneus long leg view with SPECT/CT of the affected ankle were eligible for inclusion. Primary outcome was MAJAP divided into 3 alignment categories (medial shift, neutral, lateral shift). SPECT/CT activation was determined in 8 different areas of the ankle joint. A Spearman rho correlation coefficient was calculated to investigate the relationship between the alignment categories and SPECT/CT activation in the 8 areas. Forty-nine patients (mean age 58.8 [SD 10.0] years) with 52 ankles with moderate to severe asymmetric OA were included. A significantly (Spearman rho -0.379 [P = .006] and Spearman rho -0.279 [P = .045]) higher proportion of ankles with radioisotope uptake in the anteromedial ankle joint areas (zones 1 and 5) was seen in the medial shift category. A significantly (Spearman rho .312 (P = .025)) higher proportion of ankles with radioisotope uptake in the anterolateral ankle joint area (zone 8) was seen in the lateral shift category. We found in this patient group that the area of SPECT/CT uptake in asymmetric ankle OA was associated to MAJAP measured on hip-to-calcaneus weightbearing views, although the strength of the correlation is weak to moderate. Consequently, nonweightbearing metabolic SPECT/CT radiotracer uptake has the potential to help determine the area to unload in ankle joint-preserving alignment surgery.

Surfactant-Driven Dynamic Changes in Rheology of Activated Carbon Slurry Electrodes.

Carbon black slurry electrodes are an effective means to improve flow battery performance by increasing the active surface area necessary for electrochemical reactions with a cost-effective material. Current challenges with this specific flow battery chemistry include the stability and flowability of the carbon black suspensions, especially in response to formulation choices. Advancing the manufacturing, operation, and performance of these redox flow batteries requires a deeper understanding of how slurry formulation impacts its rheological profile and ultimately battery performance. In response to this need, the linear and nonlinear rheological responses of activated carbon (AC) based slurry electrode materials used in an all-iron flow battery in the presence of a nonionic surfactant (Triton X-100) were measured. Results from these measurements show the slurry is a colloidal gel with elasticity remaining constant despite increasing surfactant concentration until α (= Csurf/CAC) < 0.65. However, at α ≥ 0.65, the slurry abruptly transitions to a fluid with no measurable yield stress. This critical surfactant concentration at which the rheological profile undergoes a dynamic change matches the concentration found previously for gel collapse of this system. Moreover, this transition is accompanied by a complete loss of electrical conductivity. From these data we conclude the site specific adsorption of surfactant molecules often used in slurry formulation has a significant and dramatic impact on the stability and flowability of these suspensions. Work presented herein demonstrates the importance of additive choices when formulating a slurry electrode.

Anionic Metal-Organic Framework Derived Cu Catalyst for Selective CO2 Electroreduction to Hydrocarbons.

Metal-organic frameworks (MOFs)-related Cu materials are promising candidates for promoting electrochemical CO2 reduction to produce valuable chemical feedstocks. However, many MOF materials inevitable undergo reconstruction under reduction conditions; therefore, exploiting the restructuring of MOF materials is of importance for the rational design of high-performance catalyst targeting multi-carbon products (C2). Herein, a facile solvent process is choosed to fabricate HKUST-1 with an anionic framework (a-HKUST-1) and utilize it as a pre-catalyst for alkaline CO2RR. The a-HKUST-1 catalyst can be electrochemically reduced into Cu with significant structural reconstruction under operating reaction conditions. The anionic HKUST-1 derived Cu catalyst (aHD-Cu) delivers a FEC2H4 of 56% and FEC2 of ≈80% at -150mAcm-2 in alkaline electrolyte. The resulting aHD-Cu catalyst has a high electrochemically active surface area and low coordinated sites. In situ Raman spectroscopy indicates that the aHD-Cu surface displays higher coverage of *CO intermediates, which favors the production of hydrocarbons.

Enhanced Electrocatalysis on Copper Nanostructures: Role of the Oxidation State in Sulfite Oxidation.

The influence of surface morphology and the oxidation state on the electrocatalytic activity of nanostructured electrodes is well recognized, yet disentangling their individual roles in specific reactions remains challenging. Here, we investigated the electrooxidation of sulfite ions in an alkaline environment using cyclic voltammetry on copper oxide nanostructured electrodes with different oxidation states and morphologies but with similar active areas. To this aim, we synthesized nanostructured Cu films made of nanoparticles or nanorods on top of glassy carbon electrodes. Our findings showed an enhanced sensitivity and a lower detection threshold when utilizing Cu(I) over Cu(II). Density functional theory-based thermochemical analysis revealed the underlying oxidation mechanism, indicating that while the energy gain associated with the process is comparable for both oxide surfaces, the desorption energy barrier for the resulting sulfate molecules is three times higher on Cu(II). This becomes the limiting step of the reaction kinetics and diminishes the overall electrooxidation efficiency. Our proposed mechanism relies on the tautomerization of hydroxyl groups confined on the surface of Cu-based electrodes. This mechanism might be applicable to electrochemical reactions involving other sulfur compounds that hold technological significance.

Anisotropic phonon dynamics in Dirac semimetal PtTe2 thin films enabled by helicity-dependent ultrafast light excitation

Coherent phonons have aroused considerable attention in condensed matter physics owing to their extraordinary capacity of reflecting and controlling the physical properties of matter. However, the investigation on the interaction between coherent phonons and other microscopic particles on the ultrafast timescale within topological systems continues to be an active and unresolved area. Here, we show the energy transfer of coherent optical phonons (COP) in Dirac semimetal PtTe2 thin films using ultrafast optical pump-probe spectroscopy. Specifically, the helicity-dependent light-driven anisotropic COP signals disclose their direct connection with the light-excited anisotropic spin-polarized electrons via an angular momentum transfer. Furthermore, we observe the notable decreases in the COP oscillation frequency and the decay rate with increasing temperatures due to the anharmonic phonon-phonon scattering and electron-phonon scattering in the COP dissipation process, respectively. Our work paves the way for uncovering the coherent phonons in Dirac semimetals for the potential applications in optoelectronics and opto-spintronics.