Nature Of Reaction Research Articles

Non-reactive biochar and Bacillus pumilus RSB17-based healing powder: A sustainable solution for enhanced bacterial viability in self-healing mortar.

Existing mortar uses self-healing powders that are based on mineral admixtures, whose reactive nature negatively impacts bacterial viability and diminishes their effectiveness over time. This study aims to develop non-reactive, sustainable biochar-based healing powders with extended bacterial viability to serve as self-healing admixture in bio-mortar. Biochar from coconut husk, coconut shell, and coconut leaf petiole was evaluated for compatibility with Bacillus pumilus RSB17, emphasizing bacterial growth and calcium carbonate precipitation. Coconut shell biochar demonstrated superior performance and was used to formulate a microbial biochar healing powder. Another healing powder was prepared by lyophilizing the bacterial spore solution without protectants. The shelf life was evaluated for 180days at 4°C and 25°C, demonstrating that microbial biochar healing powder at 4°C maintained bacterial viability above the 4.5 log CFU/g threshold necessary for effective calcium carbonate precipitation, while lyophilized spore powder stored at 25°C dropped below the threshold at 90days. Microbial biochar healing powder stored at 4°C for 180days was integrated into the mortar, which healed crack width up to 0.80mm at 56days under submerged rainwater maintained at 27°C±2°C and 85%±5% relative humidity. Electrical resistivity decreased from 28.16Ω·m to 21.35Ω·m, the permeability coefficient dropped from 153.90mm/s to 0mm/s, and compressive strength regained 90.53%, which collectively indicated enhanced self-healing. Microstructural analysis confirmed the stable cuboid calcite crystals with a crystallite size of 86.62nm. Thus, Microbial biochar healing powder produced from coconut shell biochar and Bacillus pumilus RSB17 and stored at 4°C is an effective self-healing admixture for bio-mortar applications with a minimum storage period of 180days.

Validation of a laboratory spray generation system and its use in a comparative study of hexamethylene diisocyanate (HDI) evaluation methods.

Isocyanates are well-known irritants and sensitizers, and measuring their occupational airborne exposure is challenging due to their high chemical reactivity and semi-volatile nature. This study builds on a previous publication by our team that focused on comparing evaluation methods for isocyanates. The current research aims at developing, validating, and applying a laboratory generation system designed to replicate real-world conditions for spraying clear coats in autobody shops using hexamethylene diisocyanate (HDI)-based products. The system involved a spray gun connected to two chambers in series, enabling sample collection and analysis. The system successfully generated HDI and isocyanurate concentrations ranging from 0.008 to 0.040 mg m-3 and 0.351 to 3.45 mg m-3, respectively, with spatial homogeneity (RSD) of 5.8% and 16.5%. The particle-size distribution (MMAD) of 4 μm was measured using a cascade impactor and an electrical low-pressure impactor. The samples generated were used to correlate the amount of isocyanates collected with scanning electron microscope images of droplets on a filter. Three methods were compared to the reference method-an impinger with a backup glass fibre filter (GFF) and 1,2-methoxyphenylpiperazine (MP) based on ISO 16702/MDHS 25-in six generation experiments: (1) Swinnex cassette 13 mm GFF MP (MP-Swin); (2) closed-face cassette 37 mm GFF (end filter and inner walls) MP (MP-37); and (3) denuder and GFF dibutylamine (DBA) (ISO 17334-1 Asset). The analysis revealed clear trends regarding which sampler sections collected HDI (mainly in the vapor phase) or isocyanurate (exclusively in the particulate phase). The study found no significant bias between the tested methods (MP-Swin, MP-37, and Asset) and the reference method (impinger) for both HDI monomer and isocyanurate. The three tested methods showed limits of agreement beyond the acceptable range of ±30% (95% confidence interval), largely due to data variability, though MP-Swin and MP-37 exhibited lower variability than Asset. The results will be further evaluated in a real-world environment where similar clear coats are used.

Chemoselective Stabilized Triphenylphosphonium Probes for Capturing Reactive Carbonyl Species and Regenerating Covalent Inhibitors with Acrylamide Warheads in Cellulo.

Reactive carbonyl species (RCS) are important biomarkers of oxidative stress-related diseases because of their highly reactive electrophilic nature. Despite their potential as triggers for prodrug activation, selective labeling approaches for RCS remain limited. Here, we utilized triphenylphosphonium groups to chemoselectively capture RCS via an aqueous Wittig reaction, forming α,β-unsaturated carbonyls that enable further functionalization. We first designed native (light) and deuterated (heavy) probes to facilitate RCS metabolomic identification through distinct MS isotope patterns. This approach allowed us to capture and relatively quantify several endogenous RCS related to advanced lipoxidation/glycation end products (ALEs/AGEs). Second, we demonstrated that various endogenous RCS can trigger the in situ generation of acrylamide warheads of targeted covalent inhibitors (TCIs) with different substituents. These structural variations influence their protein binding profiles and consequently alter their cytotoxicity, which is beneficial for the development of inhibitor cocktails.

Photochemical‐, Electrochemical‐, and Photoelectrochemical‐ Catalyzed Hydrogen Atom Transfer from Aldehydes to Acyl Radicals and Their Transformations

Acyl radical has assumed an eminent position in the synthetic chemistry due to its unique and often highly reactive nature. Using aldehyde as acyl radical source does not require the prefunctionalization of substrate. Furthermore, the formation of acyl radical can be achieved through a hydrogen atom transfer (HAT) process. In recent years, photochemical‐, electrochemical‐, and photoelectrochemical‐catalyzed intermolecular HAT from aldehydes have been regarded as mild and sustainable routes for the generation of acyl radicals. Herein, we discuss some of the key advancements in the past 6 years in photo‐, electro‐, and photoelectro‐catalyzed generation of acyl radicals from aldehydes and their utilization. We also highlight the mechanistic insights that have emerged from these transformations.

A Photochemical Strategy towards Michael Addition Reactions of Cyclopropenes.

The development of Michael addition reactions to conjugated cyclopropenes is a challenge in organic synthesis due to the fleeting and reactive nature of such strained Michael acceptor systems. Herein, the development of a photochemical approach towards such conjugated cyclopropenes is reported that serves as a strategic entry point to densely functionalized cyclopropanes in a diastereoselective fashion. The process involves the light-mediated generation of transient cyclopropenyl α,β-unsaturated esters from vinyl diazo esters, followed by an organic base catalyzed nucleophilic addition of N-heterocycles to directly access β-N-heterocyclic cyclopropanoic esters. With this synergistic approach, various trisubstituted cyclopropanes bearing N-heteroaryl and N-heterocyclic rings such as indole, pyrrole, benzimidazole, isatin, pyridinone, and quinolinone were accessed efficiently in good yield and decent to good diastereoselectivities. Further, β-indolyl cyclopropanoic acids have been synthesized and were successfully evaluated as FABP-4 inhibitors. Theoretical calculations have been performed to elucidate the mechanism, which was further supported by experimental findings.

A Photochemical Strategy towards Michael Addition Reactions of Cyclopropenes

AbstractThe development of Michael addition reactions to conjugated cyclopropenes is a challenge in organic synthesis due to the fleeting and reactive nature of such strained Michael acceptor systems. Herein, the development of a photochemical approach towards such conjugated cyclopropenes is reported that serves as a strategic entry point to densely functionalized cyclopropanes in a diastereoselective fashion. The process involves the light‐mediated generation of transient cyclopropenyl α,β‐unsaturated esters from vinyl diazo esters, followed by an organic base catalyzed nucleophilic addition of N‐heterocycles to directly access β‐N‐heterocyclic cyclopropanoic esters. With this synergistic approach, various trisubstituted cyclopropanes bearing N‐heteroaryl and N‐heterocyclic rings such as indole, pyrrole, benzimidazole, isatin, pyridinone, and quinolinone were accessed efficiently in good yield and decent to good diastereoselectivities. Further, β‐indolyl cyclopropanoic acids have been synthesized and were successfully evaluated as FABP‐4 inhibitors. Theoretical calculations have been performed to elucidate the mechanism, which was further supported by experimental findings.

Hydrogen Embrittlement of Ferritic Steel 1.4104

Abstract The primary goal of this study was to investigate laboratory techniques for hydrogenating selected steels and to examine the hydrogen embrittlement of steel 1.4104. These processes, which involve hydrogenation and subsequent mechanical testing, are rarely performed in laboratories due to the need for precise, costly equipment and the inherent risks associated with hydrogen’s highly reactive and explosive nature. Various theories have been proposed to explain the mechanisms behind hydrogen embrittlement in steels. These theories attribute material degradation to hydrogen’s interaction with the steel microstructure. However, their applicability is often limited, as they are developed for specific conditions and may not fully describe the phenomenon under different scenarios. This work focused on hydrogenating steel 1.4104 using two distinct methods: immersion and cathodic. The aim was to induce embrittlement and compare the resulting fracture surfaces, particularly after conducting Charpy impact tests, to evaluate the effects of each hydrogenation method.

Unraveling the Degradation Mechanisms in Composite Solid Polymer Electrolyte through in-Situ Impedance and Ex-Situ SEM

The increasing demand for batteries with higher energy density and enhanced safety has spurred the advancement of solid-state batteries (SSBs). While SSBs offer promising pathways to surmount the limitations of conventional batteries, their widespread adoption faces hurdles, notably due to the degradation mechanisms that impair their durability and efficacy. Among these, Li metal as anode materials acclaimed for its high energy density still encounter significant challenges related to safety and stability, primarily due to its reactive nature and formation of dendrites. Although solid-state electrolytes (SSEs) are expected to inhibit Li dendrite growth, issues with interface compatibility and dendrite penetration through SSEs remain critical barriers, underscoring the complex interplay of material properties that must be addressed to realize the full potential of SSB technologies. In this study, we delve into the failure mechanisms prevalent in SSBs by analyzing the morphology of SSEs and their interactions with electrode materials over successive cycling. Employing a combination of cycling tests, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS), we investigate the degradation patterns in lithium iron phosphate (LFP) electrodes, lithium metal, and SSEs.The composite solid polymer electrolyte (CSPE) is synthesized by dissolving PVDF-HFP, PPC, and LiTFSi in DMF solvent, enriched with 10 wt% LLZO, and formed by slurry casting. Through our preliminary study, development of cracks in LFP electrodes was found mainly due to uneven Li stripping/plating. The aggregate formation of Li dendrite was also observed in the early charge/discharge cycles through ex-situ SEM. Significant increase in SSE porosity suggests Li formation and penetration into the CSPE for its low mechanical strength. The EDS analysis of CSPE at the end-of-life stage further reveals a notable shift towards carbon presence, likely indicating the formation of Li₂CO₃ after exposure of during transfer. This result signals high concentration of Li on the surface of CSPE. Further interphase information is revealed by analyzing the solid-electrolyte interphase (SEI) formation through in-situ impedance study. Our study offers critical insights into the mechanisms underlying the degradation of each component in the SSBs providing a foundational understanding necessary for the failure analysis of SSBs.

Understanding the Role of Manganese Sulfate As an Electrolyte Additive for Aqueous Zinc Ion Battery

As energy demand escalates, there is a concurrent rise in the utilization of fossil fuels, exacerbating environmental challenges. To solve this challenge and achieve sustainable development, extensive research into renewable energy options is being conducted. Unlike conventional energy sources, renewable energies like solar and wind power exhibit fluctuations. Thus, effective utilization of these sources necessitates the development of energy storage systems to ensure a reliable and consistent energy supply. Among them, rechargeable batteries have been regarded as the most favorable candidate for energy storage systems because of their long cycle life, low pollution, portability and high efficiency. Of these, lithium-ion batteries (LIBs) have long held sway in the commercial rechargeable battery market, thanks to their high energy density and extended cycle life. However, several limitations obstruct their further progress. The safety concerns arising from toxic, volatile, and flammable electrolytes pose a significant challenge. Additionally, rising lithium prices can be another obstacle. These challenges have spurred researchers to investigate alternative batteries characterized by low cost, high safety, and extended cycle life. One such promising option is the aqueous zinc-ion battery (AZIB), garnering significant interest owing to its notable benefits, including high capacity and the low redox potential of zinc metal. Moreover, the stability of zinc metal in water, in contrast to the highly reactive nature of lithium, enables the use of aqueous electrolytes, enhancing safety considerably. Among various cathode materials for ZIBs, manganese-based options stand out for their high capacity, suitable working voltage, and excellent theoretical capacity, positioning them as compelling choices. However, the MnO2 electrode often suffers from capacity degradation over cycling, primarily due to manganese dissolution. Previous studies suggest that the role of Mn2+ additive in electrolytes is that it inhibits the dissolution of manganese cathode based on Le Chatelier's principle. However, gaining a comprehensive understanding of the inhibition mechanism has been challenging due to the presence of manganese species not only in the electrolyte but also in the cathode material. In this paper, we use a simplified cell design to address this limitation. Prior to qualitative analysis, we manipulate three distinct factors to optimize conditions for subsequent experiments. Under the set conditions, qualitative analysis can be conducted using X-ray diffractometry (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and infrared spectroscopy. Furthermore, to assess their impact on electrochemical properties, cyclic voltammetry (CV) and Galvanostatic Charge/Discharge (GCD) tests are performed. This discovery is noteworthy as it challenges conventional understanding. Previous research suggested that adding Mn2+ to the electrolyte enhances cycle stability by preventing manganese dissolution. Our findings laid the groundwork for uncovering the role of the Mn2+ additive.[1] M.H. Alfaruqi, V. Mathew, J. Gim, S. Kim, J. Song, J.P. Baboo, S.H. Choi, J. Kim, Electrochemically induced structural transformation in a γ-MnO2 cathode of a high capacity zinc-ion battery system, Chem. Mater. 27 (2015) 3609-3620[2] K. Lu, B. Song, Y. Zhang, H. Ma, J. Zhang, Encapsulation of zinc hexacyanoferrate nanocubes with manganese oxide nanosheets for highperformance rechargeable zinc ion batteries, J. Mater. Chem. A. 5 (2017) 23628-23633

Three-Dimensional Imaging of Large-Volume Lithium Metal Microstructure by Xenon Plasma Focused Ion Beam

Advanced energy storage systems are increasingly in demand due to the rising needs of portable electronics, electric vehicles, and grid-scale energy storage. Lithium (Li) metal stands out as an exceptional battery anode with its high theoretical specific capacity (3860 mA g-1 compared to graphite's 372 mA g-1) and low redox potential (-3.04 V vs. the standard hydrogen electrode). However, practical Li metal anodes often face challenges such as low Coulombic efficiency, short cycle life, and safety concerns, mainly due to the reactive nature of Li metal and the unpredictable deposition with diverse morphologies.Developing advanced Li metal anodes requires a deep understanding of their electrode structure. It is indispensable to find three-dimensional (3D) images. However, obtaining accurate 3D imaging of Li anodes poses significant challenges. On one hand, the non-uniform electrodeposition of Li metal necessitates a large sample to accurately represent the entire electrode. On the other hand, achieving high resolution is essential for distinguishing the complex phases within the Li electrode, including metallic Li, solid electrolyte interphase (SEI), and pores. While popular 3D imaging technologies like X-ray computed tomography and nuclear magnetic resonance imaging offer comprehensive size information, they often struggle with limitations in resolution or imaging contrast. Traditional focused ion beam-scanning electron microscopy (FIB/SEM) can provide high-resolution images at nanoscale, but its use of gallium ion (Ga+) leads to issues such as ion implantation and limited size (≤ 10 μm). An emerging alternative, plasma FIB/SEM (PFIB/SEM), coupled with Xenon (Xe) gas, featured by both high resolution and large volume size, presents a promising solution, making it appealing for characterization of Li electrode.In this presentation, Xe PFIB is employed for 3D imaging of electrodeposited Li with a large volume (200 μm in dimension) and high resolution (50 nm per pixel). This approach facilitates the clear identification of two phases: deposited Li metal and SEI/pores. It enables the quantification of their spatial distribution, packing density, and specific surface area, crucial parameters determining the Coulombic efficiency of the deposited Li anode. Furthermore, the ability to separate individual Li particles provides quantitative information on volume size, particle number, and shape. These quantitative results establish a robust mathematical relationship with the overpotential of Li deposition, significantly enhancing our understanding of the Li electrodeposition process.Leveraging the large volume and high-resolution 3D information obtained through Xe PFIB-SEM, this work demonstrates its significance in assessing and understanding electrodeposited Li, offering valuable insights for designing advanced Li metal anodes. Xe PFIB-SEM methodology is poised to become a pivotal technique for 3D characterization in energy storage materials and related fields.

Application of UHPLC-ESI-MS/MS to Identify Free Radicals via Spin Trapping with BMPO.

Free radicals play an important role in many chemical and biological processes, but due to their highly reactive and short-lived nature, they evade most analytical techniques, limiting our understanding of their formation and reactivity. Spin trapping molecules can react with free radicals to form radical adducts with lifetimes long enough for analysis. Mass spectrometry is an attractive way to identify radical adducts, but due to their radical nature, they form untraditional oxidized [M]+ and reduced [M+2H]+ ions, which complicates the interpretation of mass spectrometry analysis. This work uses simplified mixtures of radicals generated in both water and dimethyl sulfoxide (DMSO) with spin trap 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO), to elucidate the behavior of nitroxide spin traps in electrospray ionization (ESI) mass spectrometry (MS) interfaced with liquid chromatography (LC). This study proposes a disproportionation mechanism to explain the formation of the oxidized and reduced BMPO adducts detected by LC-ESI-MS and explores the formation of "di-adducts" through radical recombination. We finally present a framework for differentiating between the different types of ions using collision induced fragmentation mass spectra (MS/MS). This work offers a comprehensive investigation into the behavior of radical adducts in ESI-MS to streamline the identification of organic radicals and advance understanding of radical chemistry.

Computational modeling of the Nb -CO chemisorption process.

The transition metal niobium (Nb) has attracted considerable attention from the scientific community due to its intriguing electronic properties and applications in catalysts suitable for chemical reactions. Thus, this work investigates the adsorption of the atmospheric polluting gas carbon monoxide (CO) by the niobium cluster (Nb ), to describe the reactive nature of Nb . This entire study was carried out by applying the Coupled-Cluster method and Density Functional Theory (through the HSE06 functional) and the def2-QZVP plus Def2-TZVP/C auxiliary basis set functions. The results of electronic structure calculations and IR vibrational spectra suggest that both Nb and the Nb -CO clusters can be considered stable. Furthermore, the obtained results also indicate that there is a chemisorption of carbon monoxide by the Nb niobium cluster. This feature can serve as motivation for future theoretical-experimental studies, as it suggests that the Nb cluster may have possible technological applications in automotive catalytic processes. Initial three-dimensional structures were constructed. Complete optimization of the geometry was performed in coupled cluster and density functional theory methods. From the optimization configuration, it was possible to investigate the stability, chemisorption process, binding energies, charge analysis, molecular orbital energies, and IR vibrational spectra of the systems.

Permeability shifts in chalk core during produced water reinjection

Chalk reservoirs, due to their high porosity and very low permeability, represent one of the most interesting cases for engineering studies of carbonates. They exhibit complex fluid-rock interactions because of their reactive surfaces and dense porous medium. The reinjection of produced water is an attractive strategy for managing wastewater flow from oil wells. However, the complex composition of produced water, the reactive nature of carbonate rocks, and their low permeability create challenges related to permeability loss.This study examines the stages of permeability change during core flooding experiments up to the point of complete clogging. A distinctive feature of this study is the presence of residual oil in the core samples, which simulates real reservoir conditions during produced water reinjection. The presence of residual oil is an additional factor influencing the change in core permeability, but there is no clear consensus in the research community on its impact on permeability during produced water injection.All experiments were conducted in a core flooding system simulating well conditions in terms of pressure (170 bar) and temperature (70 °C). Produced water samples from the Dan field were used to replicate the chemical and thermodynamic processes occurring in a real well. The experiments identified three stages of permeability change: an initial increase in permeability (+12%), a period of pressure stabilization, and a subsequent decrease in permeability (−8%) due to the formation of inorganic precipitates within the core channels.The primary objective of the experiments is to investigate the relationship between permeability changes and the stages of reinjection, with a focus on the effects of residual oil. The study focuses on identifying the processes occurring up to the point of complete clogging, considering the impact of residual oil saturation in the chalk core samples. Image analysis using scanning electron microscopy, particle size measurement with a zeta-potential meter, and thermodynamic scale formation modeling with ScaleCERE software were employed to explain these processes.Three stages of permeability change were identified during the injection of 200 pore volumes of produced water: increased permeability (+12%), pressure stabilization, and decreased permeability (−8%). The positive influence of residual oil saturation on the filtration and storage properties of the reservoir was established, due to the mobilization of chalk core particles. Additionally, the theory of core channel clogging during the reinjection of formation water by the formation of inorganic precipitates within the channels was confirmed.Understanding the causes of permeability reduction that occurred during the stage of permeability decrease enables the development of water purification methods specifically targeted at the causes of rock clogging. Predicting the process of injecting a mixture of produced and seawater will help in interpreting the data during disposal operations by injecting formation water into an injection well, and it will allow for the selection of effective measures to mitigate the impact on the reservoir.

Transforming Cybersecurity Infrastructure : A Multi-dimensional Approach to Risk, Culture, and Technological Integration

The rapid acceleration of digital transformation has exposed critical limitations in traditional cybersecurity approaches, particularly in their reactive nature and disconnection from broader organizational strategies. This article critically examines current cybersecurity practices in IT infrastructure management, identifying significant gaps in the integration of security measures with business objectives, organizational culture, and emerging technologies. Through a mixed-method analysis of industry practices and empirical data from multiple case studies, The article proposes a comprehensive framework that transcends conventional security paradigms. The article introduces a proactive, risk-based approach that integrates cultural transformation, emerging technologies, and resilience building while fostering strategic partnerships across stakeholder groups. Initial implementation across various organizational contexts demonstrates significant improvements in security posture, incident response times, and overall business alignment. The findings contribute to both theoretical understanding and practical application of integrated cybersecurity management, offering valuable insights for practitioners and researchers in the field of IT security and organizational resilience. This article addresses a critical gap in current literature by providing a holistic approach that aligns cybersecurity initiatives with organizational transformation while considering human factors and technological evolution.

Enhancing the Reactivity of an Aromatic cyclo-P5 Ligand via Electrophilic Activation.

Electrophilic activation of the aromatic cyclo-P5 ligand in [Cp*Fe(η5-P5)] is demonstrated to drastically enhance its reactivity towards weak nucleophiles. Unprecedented functionalized, contracted as well as complexly aggregated polyphosphorus compounds are accessed utilizing [Cp*Fe(η5-P5Me)][OTf] (A), highlighting the great potential of this underexplored mode of reactivity. Addition of carbenes to A affords novel 1,2- or 1,1-difunctionalized cyclo-P5 complexes [Cp*Fe(η4-P5(1-L)(2-Me)][OTf] (L=IDipp (1), EtCAAC (2), IiPr (3 b)) and [Cp*Fe(η4-P5(1-IiPr)(1-Me)][OTf] (3 a). For the first time, the much smaller IMe4 leads to the contraction of the cyclo-P5 ligand and formation of [Cp*Fe(η4-P4(1-IMe)(4-Me)] (4). DFT calculations shed light on the delicate mechanism of this type of reaction, which is reinforced by the experimental identification of key intermediates. Even the comparably weak nucleophile IDippCH2 reacts with A to form [Cp*Fe(η4-P5(1-IDippCH2)(1/2-Me)][OTf] (6 a/b), highlighting its explicitly more reactive nature. Moreover, exposure of A to IDippEH (E=N, P) leads to a unique aggregation reaction affording [{Cp*Fe}2{μ2,η4:3:1-P10Me2(IDippN)}][OTf] (8) and [{Cp*Fe}2{μ2,η4:1:1:1-P11Me2(IDipp)}][OTf] (9), respectively.

Morphological analysis and cytotoxicity of acrylamide on SPC212 human mesothelioma cells: Do low doses induce proliferation, while high doses cause toxicity?

Acrylamide is broadly utilized in numerous areas with different purposes including being an additive, flocculating, sealing, dry strength improver and polymerizing agent, and so forth. Furthermore, it forms in certain food products at high temperatures. It poses serious hazard since its readily water-soluble and very reactive nature. Besides invivo studies, several invitro studies with various cell lines are carried out to evaluate its toxicity. However, of these cell line studies, there are no mesothelium or mesothelioma cell lines. To fill this lacuna, we aimed at examining various dose range of acrylamide on SPC212 human mesothelioma cell line. First, we executed MTT and neutral red cytotoxicity tests and ascertained IC50 dose. Next, we performed inverted, light (haematoxylin-eosin and May Grünwald), fluorescent (DAPI) and confocal microscope (AO/EB) analyses as well as immunohistochemistry for Bax, Bcl-2 and PCNA proteins. As a result, we found IC50 of acrylamide at 2.65 mM. Starting from 3.13 mM of acrylamide dose, a deep decrease in cell proliferation was observed. Particularly in MTT assay, a proliferative action of acrylamide was detected at 0.39 and 0.78 mM, supported with inverted microscope images. In light microscope analysis, several cellular degenerations, including condensed and kidney-shaped nucleus were evident. In AO/EB staining, cells with apoptotic characteristics augmented dose-dependently, being upheld by a parallel uptick in Bax and a dimunition in Bcl-2 staining. Besides, PCNA decreased at IC50 dose of acrylamide. This is the acrylamide-associated first study conducted on SPC212 mesothelioma cells encompassing advanced morphological analysis. We believe this study to be an incentive for future studies.

Interconnected Stock Markets: Analysing Cointegration and Correlation among Global Stock Indices

This study examines the long-term and short-term relationships among five major global stock indices—NSE NIFTY (India), S&P 500 (USA), FTSE 100 (UK), Hang Seng (Hong Kong), and Nikkei 225 (Japan)—over the period from 2008 to 2023. Using advanced econometric techniques such as Johansen cointegration tests, Engle-Granger residual cointegration test and the Vector Error Correction Model (VECM), the research explores the degree of interconnectedness and cointegration among these indices. The results indicate strong positive correlations between NSE NIFTY, S&P 500, and Nikkei 225, suggesting a growing synchronization of these markets due to global economic integration. Johansen's test reveals the presence of multiple long-term equilibrium relationships, affirming that despite short-term deviations, these markets tend to move together in response to global macroeconomic factors. The analysis further highlights that the S&P 500 and FTSE 100 indices exhibit significant error correction mechanisms, underscoring their leadership role in global market dynamics. In contrast, NSE NIFTY shows a weaker adjustment toward long-term equilibrium, indicating its reactive nature to changes in other global indices, particularly the S&P 500. The study finds that while Hang Seng and Nikkei 225 are connected globally, their short-term linkages appear weaker, likely influenced by regional factors. Overall, the results emphasize the critical influence of the U.S. and Japanese markets on NSE NIFTY, with both long-term cointegration and short-term market dynamics shaping the Indian stock market’s movements. This research offers key insights for investors seeking to understand global stock market interdependencies and manage portfolio risk.

Unraveling the Oxygen Vacancy-Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis.

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO2.5-T), pyramidal (LaCoO2.5-P), and octahedral (LaCoO3) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO4 tetrahedron > CoO6 octahedron > CoO5 pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO4 sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO5 sites.

Nature of Reactive Sites in TS-1 from 15N Solid-State NMR and Ti K-Edge X-Ray Absorption Spectroscopic Signatures Upon Pyridine Adsorption.

Ti-containing zeotypes, notably titanosilicalite-1 (TS-1), are prominent examples of heterogeneous catalysts that have found applications in selective oxidation processes with hydrogen peroxide. Despite extensive characterization studies including using various probe molecules to interrogate the nature and the local environment of Ti sites, their detailed structure (as well as reactivity) remains elusive. Here, we demonstrate that using low temperature 15N magic angle spinning (MAS) ssNMR spectroscopy of adsorbed pyridine on TS-1 combined with Ti K-edge XANES on a range of samples (dehydrated, hydrated, contacted with H2O2 and pyridine) provides unique information regarding the Ti sites, highlighting their reactivity and dynamic nature. While dehydrated TS-1 shows only Lewis acid sites, the presence of H2O generates Brønsted acid sites, whose amount correlates with water loading. Moreover, the methodology─based on 15N ssNMR and Ti K-edge XANES─applied to a library of samples with various Ti-loadings and absence of extraframework TiO2 also enables quantification of the amount of Lewis acid sites and to establish a structure-activity descriptor (ratio of pyridine adsorbed on silanols vs titanium). Complementary analysis including computational modeling reveals that the reaction of Ti sites with H2O generates an acidic bridging silanol Ti-(OH)-Si, upon hydrolysis of one Ti-O-Si linkage, where Ti expands its coordination from four to pentacoordinated according to XAS.

Neurofeedback: potential for abuse and regulatory frameworks in the United States.

Neurofeedback is a brain-training technique that continues to develop via ongoing innovations, and that has broadening potential impact. Once confined primarily to clinical and research settings, it is increasingly being used in the general population. Such development raises concerns about the current regulatory mechanisms and their adequacy in protecting patterns of economic and political decision-making from the novel technology. As studies have found neurofeedback to change subjects' preferences and mental associations covertly, there is a possibility it will be abused for political and commercial gains. Current regulatory practices (including disclaimer requirements, unfair and deceptive trade practice statutes and undue influence law) may be avenues from which to regulate neurofeedback influence. They are, however, limited. Regulating neurofeedback will face the line-drawing problem of determining when it induces an unacceptable level of influence. We suggest experiments that will clarify how the parameters of neurofeedback training affect its level of influence. In addition, we assert that the reactive nature of the traditional models of regulation will be inadequate against this and other rapidly transforming technologies. An integrated and proactive regulatory system designed for flexibility must be adopted to protect society in this era of modern technological advancement. This article is part of the theme issue 'Neurofeedback: new territories and neurocognitive mechanisms of endogenous neuromodulation'.