Laccase Mimics: Probing the Electrocatalytic Potential for CO Reduction.

The intricate copper-based redox center in laccase serves as an exemplar for developing laccase mimics. The current need of the hour is exploring the application of these biogenic laccase mimics beyond their traditional roles in sustainable energy conversion. This study investigates the untapped potential of laccase and their biogenic copper-amino acid mimic in the context of electrochemical CO₂ reduction (ECR), leveraging the Cu/Cu redox system.

Hydroxy-substituted aromatic N-heterocycles as high-affinity CO adsorbents: a DFT study.

Hydroxy-substituted aromatic N-heterocycles, including hydroxy pyridine (py), dihydroxy naphthyridines (nt), and trihydroxy pyridonaphthyridines (pn), have been investigated for their potential as CO adsorbents using density functional theory (DFT) calculations. Building on the pioneering work of Luo , who demonstrated exceptional CO capture capacities in pyridine-containing anion-functionalized ionic liquids, this study extends the exploration to a broader range of N-heterocycles. These N-heterocycles exhibit exceptional CO capture capabilities, driven by cooperative interactions between nitrogen and oxygen centres with CO.

Substituent Effects on NMR Chemical Shifts and Cyclic Hydrogen Bonding in 2-Pyridone Dimers: An Accurate Approach to Hammett Constant Determination Linking Structure, Energetics, and Electron Distribution.

The Hammett substituent parameter () is fundamental to physical organic chemistry but often suffers from inconsistencies in experimental determination across diverse substituents. This study presents a quantum chemical approach for estimating values using H NMR chemical shift differences (Δ) in hydrogen-bonded 2-pyridone heterodimers. Using density functional theory (M06L/6-311++G(d,p)), we examined four dimer topologies─, , , and ─and found that the Δ values in the configuration, where the substituent is spatially remote from the hydrogen-bonding region, exhibit the strongest correlation with .

Artificial intelligence based malignant lymphoma type prediction using enhanced super resolution image and hybrid feature extraction algorithm.

In the medical field, the most common and frequent type of blood cancer is lymphoma. Accurately predicting and early response to lymphoma treatment will be useful for initiating treatment plans to achieve a greater rate of cure or reduced risk of treatment-related morbidity and death. Numerous research studies have revealed several pre-treatment predictive variables, including age, lactate dehydrogenase (LDH), Ann Arbor stage, and ECOG performance.

Efficacy and safety of 8-week regimens for the treatment of rifampicin-susceptible pulmonary tuberculosis (TRUNCATE-TB): a prespecified exploratory analysis of a multi-arm, multi-stage, open-label, randomised controlled trial.

Background: WHO recommends a 2-month optimal duration for new drug regimens for rifampicin-susceptible tuberculosis. We aimed to investigate the efficacy and safety of the 8-week regimens that were assessed as part of the TRUNCATE management strategy of the TRUNCATE-TB trial.

Methods: TRUNCATE-TB was a multi-arm, multi-stage, open-label, randomised controlled trial in which participants aged 18-65 years with rifampicin-susceptible pulmonary tuberculosis were randomly assigned via a web-based system, using permuted blocks, to 24-week standard treatment (rifampicin, isoniazid, pyrazinamide, and ethambutol) or the TRUNCATE management strategy comprising initial 8-week treatment, then post-treatment monitoring and re-treatment where needed.

Weak Interactions Break Strong Bonds: Noncovalent Complexes of H-X with N-Heterocycles.

The phenomenon of positive cooperativity in noncovalent complexes, arising from electron donor-acceptor (eDA) interactions and subsequent electron reorganization, has been investigated by using density functional theory (DFT) at the ωB97XD/6-311 + G(3df,2pd) level. The study focuses on the interaction of various nitrogen- and oxygen-containing heterocycles with HF and HCl molecules. The formation of dimer complexes leads to electron flow from the nitrogen lone pair to the hydrogen halide, enhancing the electron density on the halogen atom, as made evident by molecular electrostatic potential (MESP) analysis.

Unveiling the Hypervalent Electronic Structure of Main Group Zwitterions: Ylides or Ylenes? A DFT Study.

This study uses density functional theory (DFT) calculations at the M06-2X/6-311 + G(d,p) level to explore the potential of main group non-metals (X = O, N, S, P) to form hypervalent ylides (RX-YR ). Substituent effects (R = alkoxy, alkyl, phenyl, H, NH, NMe, halogens) on the stability of these ylides and their neutral counterparts (R X-YR ) are analyzed across various X → Y bonding scenarios. Fluorine-substituted ylides (e.

Ladderenes as Covalently Condensed Acetylene: A DFT Investigation of Gold(I)-Catalyzed Mechanism, Substituent Effects and Energy Storage Potential.

Ladderenes, unique polymers composed of fused cyclobutane rings, exhibit promising properties for energy storage applications, including reversible redox behavior and structural tunability. This density functional theory (DFT) study investigates the formation of ladderenes via gold(I)-catalyzed alkyne-alkene coupling reactions. Our calculations reveal a step-wise chain propagation mechanism where the alkene product of each step reacts with a ligand-gold-alkyne complex, leading to the sequential addition of cyclobutene units.

Association between thyroid dysfunction and insulin resistance: a retrospective cohort study.

Objective: To evaluate the association between thyroid disease and diabetes markers.

Design: Retrospective cohort study.

Setting: The study was conducted in a diagnostic setting where the primary care providers recommended the patients to test for thyroid and diabetes panels.

Correction: Psychological distress and burnout among healthcare worker during COVID-19 pandemic in India-A cross-sectional study.

[This corrects the article DOI: 10.1371/journal.pone.

Beyond the triple bond: unlocking dinitrogen activation with tailored superbase phosphines.

Activating atmospheric dinitrogen (N), a molecule with a remarkably strong triple bond, remains a major challenge in chemistry. This theoretical study explores the potential of superbase phosphines, specifically those decorated with imidazolin-2-imine ((ImN)P) and imidazolin-2-methylidene ((ImCH)P) to facilitate N activation and subsequent hydrazine (HNNH) formation. Using density functional theory (DFT) at the M06L/6-311++G(d,p) level, we investigated the interactions between these phosphines and N.

Sustainable sentiment analysis on E-commerce platforms using a weighted parallel hybrid deep learning approach for smart cities applications.

Sentiment analysis (SA) of several user evaluations on e-commerce platforms can be used to increase customer happiness. This method automatically extracts and identifies subjective data from product evaluations using natural language processing (NLP) and machine learning (ML) methods. These statistics may eventually reveal information on the favourable, neutral, or negative attitudes of the consumer base.

From loose to tight: unveiling bond stretch isomerism in π-complexes of Li, Na and K.

The study investigates the phenomenon of bond stretch isomerism (BSI) in complexes formed between alkali metals (Li, Na, K) and various non-aromatic, aromatic hydrocarbons, as well as heteroaromatic systems. The research employs density functional theory (DFT) calculations to optimize complex geometries and analyze their electronic structures using molecular electrostatic potential (MESP), charge, and spin density analyses. The results reveal that these complexes can exist in two distinct configurations: 'loose' long-bond isomers (lbi) that retain the original hydrocarbon geometry and 'tight' short-bond isomers (sbi) that undergo geometrical distortion upon complexation, with sbi generally being more stable.

Cooperative Noncovalent Interactions Controlling Amine-Catalyzed Aldol Reaction Pathways Catalyzed by the Bifunctional Amino Quaternary Phosphonium Ion.

Members of a new class of bifunctional amino quaternary phosphonium salts have been synthesized and utilized as catalysts in aldol condensation reactions, as demonstrated herein. These secondary amines feature a phosphonium ion connected by a carbon chain, enabling the quaternary phosphonium ion to engage in distinct cooperative noncovalent interactions. These interactions work in tandem to stabilize different transition state complexes, exclusively controlling competing amine-catalyzed aldol pathways via the Mannich mechanism.

Gold(I) Catalysis in Alkyne-Alkene Reactions: A Systematic Exploration through Molecular Electrostatic Potential Analysis.

Gold catalysis enables selective chemical transformations with catalytic activity tunable through ligand selection. This study uses the density functional theory (DFT) to explore the impact of phosphine ligands (PR) on gold(I)-catalyzed alkyne-alkene cyclobutene formation. We analyze the following key steps: (i) PR-Au complexation, (ii) alkyne binding, (iii) alkene binding, (iv) C-C coupling transition state, (v) cyclobutene formation transition state, and (vi) cyclobutene dissociation.

Infant Cervical Vestibular Evoked Myogenic Potentials: A Scoping Review.

Objectives: Children diagnosed with hearing loss typically demonstrate increased rates of vestibular loss as compared with their peers, with hearing within normal limits. Decreased vestibular function is linked with delays in gross motor development, acquisition of gross motor skills, and academic challenges. Timely development of sitting and walking gross motor skills aids in the progress of environmental exploratory activities, which have been tied to cognitive, language, and vocabulary development.

Direct Estimation of Aromatization Energy from H NMR and UV-Vis Absorption Data of Homodesmotic Molecules.

This study delves into the ring-opening reaction of two distinct diaryl-ring-pyran systems, referred to as and , where the term 'ring' encompasses aromatic, nonaromatic, or antiaromatic motifs. These systems transform into the corresponding quinonoid systems, denoted as - and -. Homodesmotic pairs (, ) and (-, -) are categorized as (aromatic, nonaromatic), (aromatic, partially aromatic), (antiaromatic, nonaromatic), and (nonaromatic, nonaromatic), with their energy difference representing aromatization energy ().

Assessing the Utility, Impact, and Adoption Challenges of an Artificial Intelligence-Enabled Prescription Advisory Tool for Type 2 Diabetes Management: Qualitative Study.

Background: The clinical management of type 2 diabetes mellitus (T2DM) presents a significant challenge due to the constantly evolving clinical practice guidelines and growing array of drug classes available. Evidence suggests that artificial intelligence (AI)-enabled clinical decision support systems (CDSSs) have proven to be effective in assisting clinicians with informed decision-making. Despite the merits of AI-driven CDSSs, a significant research gap exists concerning the early-stage implementation and adoption of AI-enabled CDSSs in T2DM management.

Improving treatment adherence among tuberculosis patients through evening DOTS in Chennai, India.

Background Fixed days and timings of service are challenges in the care of patients with tuberculosis (TB). We assessed whether provision of evening DOTS (directly observed treatment, short course) improves treatment outcomes in a city with a working population. Methods We enrolled new adult patients with TB from seven tuberculous units (TUs) in this prospective cohort study.

O-phthalaldehyde based quantification of polysaccharide modification in conjugate vaccines.

Polysaccharide-based vaccines cannot stimulate long-lasting immune response in infants due to their inability to elicit a T-cell-dependent immune response. This has been addressed using conjugation technology, where conjugates were produced by coupling a carrier protein to polysaccharides using different conjugation chemistries, such as cyanylation, reductive amination, ethylene diamine reaction, and others. Many glycoconjugate vaccines that are manufactured using different conjugation technologies are already in the market for neonates, infants and young children (e.

Utilization of the through-space effect to design donor-acceptor systems of pyrrole, indole, isoindole, azulene and aniline.

Molecular electrostatic potential (MESP) topology analysis reveals the underlying phenomenon of the through-space effect (TSE), which imparts electron donor-acceptor properties to a wide range of chemical systems, including derivatives of pyrrole, indole, isoindole, azulene, and aniline. The TSE is inherent in pyrrole owing to the strong polarization of electron density (PoED) from the formally positively charged N-center to the CC bonding region. The N → CC directional nature of the TSE has been effectively employed to design molecules with high electronic polarization, such as bipyrroles, polypyrroles, phenyl pyrroles, multi-pyrrolyl systems and N-doped nanographenes.

Unraveling pnicogen bonding cooperativity: Insights from molecular electrostatic potential analysis.

A theoretical investigation on the cooperativity of a series of binary, ternary, and quaternary complexes interconnected by pnicogen bonds has been conducted using calculations at the M06-2X/aug-cc-pVTZ level of density functional theory. By measuring changes in the molecular electrostatic potential (MESP) at the nucleus of interacting atoms in all of the complexes, it is possible to quantify the substantial reorganization of the electron density triggered by the formation of pnicogen bonds. The positive change in MESP, indicating a loss of electron density from the donor molecule in a dimer, facilitates the acceptance of electron density from a third molecule, resulting in the formation of a ternary complex with a stronger pnicogen bond compared to the one present in the binary complex.

Topology of electrostatic potential and electron density reveals a covalent to non-covalent carbon-carbon bond continuum.

The covalent and non-covalent nature of carbon-carbon (CC) interactions in a wide range of molecular systems can be characterized using various methods, including the analysis of molecular electrostatic potential (MESP), represented as (), and the molecular electron density (MED), represented as (). These techniques provide valuable insights into the bonding between carbon atoms in different molecular environments. By uncovering a fundamental exponential relationship between the distance of the CC bond and the highest eigenvalue () of () at the bond critical point (BCP), this study establishes the continuum model for all types of CC interactions, including transition states.

Comparison of Norepinephrine and Terlipressin vs Norepinephrine Alone for Management of Septic Shock: Few Concerns.

: Khera D, Suresh C. Comparison of Norepinephrine and Terlipressin vs Norepinephrine Alone for Management of Septic Shock: Few Concerns. Indian J Crit Care Med 2023;27(8):605.