Binding the Power of Cycloaddition and Cross-Coupling in a Single Mechanism: An Unexpected Bending Journey to Radical Chemistry of Butadiynyl with Conjugated Dienes.

What if an experiment could combine the power of cycloaddition and cross-coupling with the formation of an aromatic molecule in a single collision? Crossed molecular beam experiments augmented with electronic structure and statistical calculations provided compelling evidence on a novel radical route involving 1,3-butadiynyl (HCCCC; X∑) radicals synthesizing (substituted) arylacetylenes in the gas phase upon reactions with 1,3-butadiene (CHCHCHCH; XA) and 2-methyl-1,3-butadiene (isoprene; CHC(CH)CHCH; XA'). This elegant mechanism merges two previously disconnected concepts of cross-coupling and cycloaddition-aromatization in a single collision event via the formation of two new C(sp)-C(sp) bonds and bending the 180° moiety of the linear 1,3-butadiynyl radical out of the ordinary by 60° to 120°. In addition to its importance to fundamental organic chemistry, this unconventional mechanism links two previously separated routes of gas-phase molecular mass growth processes of polyacetylenes and polycyclic aromatic hydrocarbons (PAHs), respectively, in low-temperature environments such as in cold molecular clouds like the Taurus Molecular Cloud (TMC-1) and in hydrocarbon-rich atmospheres of planets and their moons such as Titan, which revises the established understanding of low-temperature molecular mass growth processes in the Universe.

25-Hydroxycholesterol modulates synaptic vesicle endocytosis at the mouse neuromuscular junction.

Many synaptic vesicles undergo exocytosis in motor nerve terminals during neuromuscular communication. Endocytosis then recovers the synaptic vesicle pool and presynaptic membrane area. The kinetics of endocytosis may shape neuromuscular transmission, determining its long-term reliability.

High-Resolution NMR of the Hydrogenation Reaction with Parahydrogen in an Inhomogeneous Magnetic Field.

Nuclear magnetic resonance is extremely attractive for operando studies of chemical reactors. However, the heterogeneous catalyst particles placed inside an NMR probe greatly affect the uniformity of the magnetic field. This problem is especially acute when studying heterogeneous hydrogenation processes using parahydrogen.

Clinical and Diagnostic Value of ABCDE Stress Echocardiography With Exercise in Patients With Myocardial Infarction.

Aim: Evaluation of the clinical and diagnostic role of stepwise stress echocardiography (Stress Echo) with exercise using the ABCDE protocol in patients with myocardial infarction (MI).

Material And Methods: This single-site study included 75 patients (mean age 61.6±9.

The Frequency of Occurrence of Cardiovascular Risk Factors and Awareness оf Them Among Young People in Higher Education Institutions.

Objective: To assess the prevalence of risk factors  of cardiovascular disease (CV RF) development and awareness of them among young people studing at University.

Material And Methods: Сross-sectional study study included 1182 young men and women studying at Lomonosov Moscow State University (age 18-44 years), with no history of chronic non-infectious diseases, who underwent a screening  in April-June 2022. All participants filled out the standard "Questionnaire for citizens under the age of 65 years to identify chronic non-communicable diseases, risk factors for their development, and the use of narcotic drugs and psychotropic substances without prescription", a specially designed questionnaire on socio-demographic characteristics and risk factors for CVD development, and a questionnaire on nighttime sleep status.

Osteoperiosteal Cylindrical Iliac Bone Graft and Minced Cartilage as an Osteochondral Autograft for a Large Osteochondral Lesion.

Mosaicplasty is a relatively challenging procedure used in the management of focal osteochondral lesions of the joints. Donor-site morbidity is still the main concern after mosaicplasty because it entails the harvesting of an osteochondral autograft from an otherwise healthy region to be impacted later on the weight-bearing damaged site. We describe a possible alternative to conventional mosaicplasty with subchondral bone support harvested from the iliac crest as an osteoperiosteal autograft and covered with a minced cartilage layer.

Methane to Methanol Transformation on Cu/H-ZSM-5 Zeolite. Characterization of Copper State and Mechanism of the Reaction.

Cu-modified zeolites provide methane conversion to methanol with high selectivity under mild conditions. The activity of different Cu-sites for methane transformation is still under discussion. Herein, ZSM-5 zeolite has been loaded with Cu cations (1.

Periodic and Aperiodic Components of Subthalamic Nucleus Activity Reflect Different Aspects of Motor Impairment in Parkinson's Disease.

Excessive beta oscillations in the subthalamic nucleus are established as a primary electrophysiological biomarker for motor impairment in Parkinson's disease and are currently used as feedback signals in adaptive deep brain stimulation systems. However, there is still a need for optimization of stimulation parameters and the identification of optimal biomarkers that can accommodate varying patient conditions, such as ON and OFF levodopa medication. The precise boundaries of 'pathological' oscillatory ranges, associated with different aspects of motor impairment, are still not fully clarified.

Real-world effectiveness of intravenous belimumab in adults with systemic lupus erythematosus: results of the observational OBSErve study in the Russian Federation.

Background: The real-world effectiveness of intravenous (IV) belimumab in treating systemic lupus erythematosus (SLE) has been demonstrated in various countries through the OBSErve (evaluation Of use of Belimumab in clinical practice SEttings) program. Here we describe the clinical effectiveness of IV belimumab for treating SLE in real-world clinical practice in the Russian Federation.

Methods: In the retrospective, observational OBSErve Russia study (GSK Study 215349), eligible physicians enrolled adults with SLE receiving IV belimumab as part of their standard care.

Chemically Hydrophobic and Structurally Antireflective Nanocoatings in Butterflies.

Moth-eye nanostructures, known for their biological antireflective properties, are formed by a self-assembly mechanism. Understanding and replicating this mechanism on artificial surfaces open avenues for the engineering of bioinspired multifunctional nanomaterials. Analysis of corneal nanocoatings from butterflies of the genus reveals a variety of nanostructures with uniformly strong antiwetting properties accompanied by varying antireflective functionalities.

Enterobactin inhibits microbiota-dependent activation of AhR to promote bacterial sepsis in mice.

Sepsis is a major cause of morbidity and mortality, but our understanding of the mechanisms underlying survival or susceptibility is limited. Here, as pathogens often subvert host defence mechanisms, we hypothesized that this might influence the outcome of sepsis. We used microbiota analysis, faecal microbiota transplantation, antibiotic treatment and caecal metabolite analysis to show that gut-microbiota-derived tryptophan metabolites including indoles increased host survival in a mouse model of Serratia marcescens sepsis.

Hippocampal dendritic spines store-operated calcium entry and endoplasmic reticulum content is dynamic microtubule dependent.

One of the mechanisms of calcium signalling in neurons is store-operated calcium entry (SOCE), which is activated when the calcium concentration in the smooth endoplasmic reticulum (ER) decreases and its protein-calcium sensor STIM (stromal interacting molecule) relocate to the endoplasmic reticulum and plasma membrane junctions, forms clusters and induces calcium entry. In electrically non-excitable cells, STIM1 is coupled with the positive end of a tubulin microtubule through interaction with EB1 (end-binding) protein, which controls its oligomerization, SOCE and participates in ER movement. STIM2 homologue, which is specific for mature hippocampal dendritic spines, is known to interact with EB3 protein, however, not much is known about the role of this interaction in STIM2 clustering or ER trafficking in neurons.

Optimizing concrete sustainability with bagasse ash and stone dust and its impact on mechanical properties and durability.

Addressing environmental challenges such as pollution and resource depletion requires innovative industrial and municipal waste management approaches. Cement production, a significant contributor to greenhouse gas emissions, highlights the need for eco-friendly building materials to combat global warming and promote sustainability. This study evaluates the simultaneous use of Sugarcane Bagasse Ash (SCBA) and Stone Dust (SD) as partial replacements by volume for cement and sand, respectively, at varying ratios in eco-strength concrete mixes designed for 28 MPa (ES-28) and 34 MPa (ES-34), emphasizing their economic and environmental benefits.

Cholesterol-ester prevents lipoprotein core from solidifying: Molecular dynamics simulation.

As an important part of lipid metabolism the liver produces large particles called very low density lipoproteins, filled mostly with triglyceride and cholesterol esters mixture. A large percentage of the mixture composition components has a melting point above physiological temperature. Thus solid cluster formation or phase transition could be expected.

Bone health ECHO case report: High bone mass in a patient with chronic kidney disease.

Bone Health ECHO (Extension of Community Healthcare Outcomes) is a growing family of online educational programs. Its mission is to enhance delivery of best practice skeletal healthcare worldwide. Each program typically consists of a didactic lecture and discussion of clinical cases with diagnostic and treatment dilemmas.

Bone Health ECHO Case Report: Rare Cases of Hypophosphatemia and Low-Traumatic Fractures in Patients with Type 1 Diabetes Mellitus.

Bone Health ECHO (Extension of Community Healthcare Outcomes) is a virtual community of practice that has been connecting healthcare professionals online once weekly for the past 10 years. A key component of each ECHO session is presentation and discussion of patient cases with diagnostic and treatment dilemmas. Here we present two wheelchair-bound female patients aged 47 years (Patient 1) and 34 years (Patient 2), both with type 1 diabetes mellitus (T1DM).

The impacts of the COVID-19 pandemic on the burden of maternal and neonatal disorders: A counterfactual modeling based on the global burden of disease study (2021).

Objectives: During the COVID-19 pandemic, global health systems faced unprecedented challenges, as well as in maternal and neonatal health, thus this study aims to clarify the impacts of COVID-19 on maternal and neonatal disorders (MNDs), regional variations, and the role of economic support.

Methods: We have developed a counterfactual model integrating Autoregressive Integrated Moving Average and Long Short-Term Memory models to forecast the burden of MNDs from 2020 To et al., 2021, which was compared with the actual burden to quantify the specific impact of the COVID-19 pandemic on MNDs.

Regional green economies and Bitcoin's electricity consumption: Paving the way for global sustainability.

In the context of global sustainability goals, it is imperative to examine the interplay between emerging financial technologies and environmental objectives, which in turn offers insights into the implications of such technologies on sustainable investments and environmental policy decisions. Accordingly, this study investigates the influence of Bitcoin's energy consumption (BEC), as a representative of the cryptocurrency market, on the regional green economy indices of the United States, Europe, and Asia. Utilizing both unfiltered and filtered data, we conduct empirical analyses from both static and dynamic perspectives to account for the causal relationships that emerged during critical market developments, employing novel algorithms including forward recursive, rolling windows, and recursive rolling.

Pharmacokinetic and Pharmacodynamic Equivalence of Biosimilar and Reference Ultra-Rapid Lispro: A Comparative Clamp Study in Healthy Volunteers.

Ultra-rapid insulin lispro is an innovative insulin analogue designed to achieve rapid onset and short duration of action, aimed at optimizing glycemic control in patients with diabetes. This was a double-blind, randomized, 2-period, crossover clamp study to evaluate the pharmacokinetics (PK) and pharmacodynamics (PD), along with safety profiles, of a potential biosimilar ultra-rapid insulin lispro compared to the reference product in healthy White men. A total of 35 healthy volunteers completed hyperinsulinemic euglycemic clamp procedures across both study periods.

Nucleophilic Functionalization of a Cationic Pentaphosphole Complex-A Systematic Study of Reactivity.

The systematic nucleophilic functionalization of the cationic pentaphosphole ligand complex [Cp*Fe(η-PMe)][OTf] (A) with group 16/17 nucleophiles is reported. This method represents a highly reliable and versatile strategy for the design of novel transition-metal complexes featuring twofold substituted end-deck cyclo-P ligands, bearing unprecedented hetero-element substituents. By the reaction of A with classical group 16 nucleophiles, complexes of the type [Cp*Fe(η-PMeE)] (E=OEt (1), OBu (2), SPh (3), SePh (4)) are obtained.

Changes in Levels of MiR-21, MiR-27a, MiR-221, and MiR-429 in the Thymus after Photodynamic Therapy and Surgical Treatment of Breast Cancer in Female Wistar Rats.

We studied the expression levels of microRNAs (miR-21, miR-27a, miR-221, and miR-429) in the thymus of female Wistar rats after surgical treatment of breast cancer (BC) and after photodynamic therapy for BC followed by tumor resection. In the group without treatment, the levels of pro-oncogenic miR-21, miR-27a, and miR-221 in the thymus were reduced in comparison with those in the group of intact control. After surgical treatment of BC, the levels of miR-21 and miR-27a in the thymus increased in comparison with those in BC without treatment.

Potential Corrosion Inhibition Properties of Flavone Derivatives on the Cu(111) Surface: A Combined DFT and Monte Carlo Simulation Study.

Since corrosion causes significant harm to the environment and economy, sustainable corrosion inhibitors are essential. This study set out to examine Anti-corrosion ability of a number of closely related polycyclic compounds of flavone derivatives, namely 5,7-dimethoxyflavone (1), 4',5,7-trimethoxyflavone (2), 3',4',5'-trimethoxyflavone (3), 5-hydroxy-3,3',4',7-tetramethoxyflavone (4), tangeretin (5), 3,3',4',5,6,7,8-heptamethoxyflavone (6), 3',5,7-trihydroxy-4',5',6-trimethoxyflavone (7) and 3',4',5,7-tetrahydroxy-3,6,8-trimethoxyflavone (8), using the DFT/B3LYP/6-311 + + G(d, p) basis set. Monte Carlo simulations were used to reveal the adsorption of the investigated compounds on the Cu(111) surface.

Unveiling the unusual i-motif-derived architecture of a DNA aptamer exhibiting high affinity for influenza A virus.

Non-canonical nucleic acid structures play significant roles in cellular processes through selective interactions with proteins. While both natural and artificial G-quadruplexes have been extensively studied, the functions of i-motifs remain less understood. This study investigates the artificial aptamer BV42, which binds strongly to influenza A virus hemagglutinin and unexpectedly retains its i-motif structure even at neutral pH.

Paired nerve stimulation with selective compensation effect.

Background: In this study we investigate the selective compensation of paired peripheral nerves in healthy humans, focusing on distinct axonal conduction velocities in different fibre types. Using paired associative stimulation (PAS) with adjustable parameters, we aimed to modulate and compensate for neuronal activity along the median nerve.

Methods: Six healthy volunteers (3 male, 3 female, aged: 22-49) participated in the current study.