Alkyl 4-Alkoxyvalerates: Characterization and Application in Pd-Catalyzed Aminocarbonylation of Iodo(hetero)arene Compounds.

The palladium-catalyzed aminocarbonylation is one of the most effective methods for the synthesis of carboxamides having great importance. Replacing fossil-based organic solvents in this routinely used catalytic protocol with biomass-derived media is crucial for developing environmentally safe alternatives and towards sustainability considerations. In this study, the open-chain derivatives of bio-originated substance g-valerolactone i.

Effect of the Protic vs. Non-Protic Molecular Environment on the to Conformation Change of Phototrexate Drug.

The therapeutical applicability of the anticancer drug phototrexate, a photoswitchable derivative of the antimetabolite dihydrofolate reductase inhibitor methotrexate, highly depends on the stability of its bioactive isomer. Considering that only the configuration of phototrexate is bioactive, in this work, the effect of the molecular environment on the stability of the isomer of this drug has been investigated. UV-vis absorption and fluorescence-based solvent relaxation methods have been used.

Palladium-Catalyzed Selective Carbonylation Reactions of -Phenylene Dihalides with Bifunctional ,-Nucleophiles.

Palladium-catalyzed carbonylation reactions of -phenylene dihalides were studied using aminoethanols as heterobifunctional ,-nucleophiles. The activity of aryl-iodide and -bromide as well as the chemoselective transformation of amine and hydroxyl functionalities were studied systematically under carbonylation conditions. Aminocarbonylation can be selectively realized under optimized conditions, enabling the formation of amide alcohols, and the challenging alkoxycarbonylation can also be proved feasible, enabling amide-ester production.

A Facile Route to Flavone-3-Carboxamides and Flavone-3-Carboxylates via Palladium-Catalyzed Amino- and Aryloxy-Carbonylation Reactions.

A library of C-3 functionalized flavones was successfully provided via palladium-catalyzed amino- and aryloxycarbonylation reactions of 3-iodoflavone (), under mild conditions. This methodology showed good functional group tolerance using a variety of amines and phenols, under an atmospheric pressure of carbon monoxide as a carbonyl source. While the flavone-3-carboxamides () were produced in 22-79%, the flavone-3-carboxylates () were obtained in excellent yields (up to 88%), under identical reaction conditions, just by switching -nucleophiles to -nucleophiles.

Boronic acid inhibitors of penicillin-binding protein 1b: serine and lysine labelling agents.

Penicillin-binding proteins (PBPs) contribute to bacterial cell wall biosynthesis and are targets of antibacterial agents. Here, we investigated PBP1b inhibition by boronic acid derivatives. Chemical starting points were identified by structure-based virtual screening and aliphatic boronic acids were selected for further investigations.

Neural-Net Artificial Pancreas: A Randomized Crossover Trial of a First-in-Class Automated Insulin Delivery Algorithm.

Automated insulin delivery (AID) is now integral to the clinical practice of type 1 diabetes (T1D). The objective of this pilot-feasibility study was to introduce a new regulatory and clinical paradigm-a Neural-Net Artificial Pancreas (NAP)-an encoding of an AID algorithm into a neural network that approximates its action and assess NAP versus the original AID algorithm. The University of Virginia Model-Predictive Control (UMPC) algorithm was encoded into a neural network, creating its NAP approximation.

An Evaluation of Messages to Promote Parental Intent to Vaccinate Children Aged <12 Years Against COVID-19.

Objectives: Effective health communication can increase intent to vaccinate. We compared 8 messages that may influence parents' intent to vaccinate their children against COVID-19.

Methods: In a cross-sectional survey of adults in the United States administered online in August 2021, 1837 parents and legal guardians were exposed to 8 messages (individual choice, gain/practical benefits, nonexpert, health care provider recommendation, altruism/community good, safety/effectiveness, safety, and effectiveness) to determine message reception and influence on intent to vaccinate their children.

Synthesis of Chroman-2,4-diones via Ring-Opening/Ring-Closing Reaction Involving Palladium-Catalyzed Intramolecular Aryloxycarbonylation.

Palladium-catalyzed aminocarbonylation of 3-iodochromone was studied in the presence of primary and secondary amines using atmospheric pressure of carbon monoxide as a carbonyl source. This procedure successfully provided a library of chromone-3-carboxamides and 3-substituted chroman-2,4-diones in 40 to 92% isolated yields. The reaction proceeded via highly chemoselective aminocarbonylation (up to 100%) in the presence of secondary amines by using monodentate or bidentate phosphine ligands.

On-DNA Synthesis of Multisubstituted Indoles.

The increasing role of the DNA-encoded library technology in early phase drug discovery represents a significant demand for DNA-compatible synthetic methods for therapeutically relevant heterocycles. Herein, we report the first on-DNA synthesis of multisubstituted indoles via a cascade reaction of Sonogashira coupling and intramolecular ring closure. Further functionalization by Suzuki coupling at the third position exploits a diverse chemical space.

COVID-19 Vaccine Hesitancy Among US Adults: Safety and Effectiveness Perceptions and Messaging to Increase Vaccine Confidence and Intent to Vaccinate.

Objective: Public health agencies have a critical role in providing effective messaging about mitigation strategies during a public health emergency. The objectives of this study were (1) to understand perceptions of COVID-19 vaccines, including concerns about side effects, safety, and effectiveness and how these perceptions influence vaccine decision-making among US adults and (2) to learn what messages might motivate vaccine uptake.

Methods: In April and May 2021, we conducted 14 online focus groups with non-Hispanic English-speaking and English- and Spanish-speaking Hispanic adults (N = 99) not vaccinated against COVID-19.

Molecular Mechanism of Labelling Functional Cysteines by Heterocyclic Thiones.

Heterocyclic thiones have recently been identified as reversible covalent warheads, consistent with their mild electrophilic nature. Little is known so far about their mechanism of action in labelling nucleophilic sidechains, especially cysteines. The vast number of tractable cysteines promotes a wide range of target proteins to examine; however, our focus was put on functional cysteines.

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles.

Palladium-catalyzed amino- and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity.

A New Application of Spin and Fluorescence Double-Sensor Molecules.

EPR imaging techniques are known to be successful tools for mapping living bodies, especially because of the high transparency of tissues in the microwave range. This technique assumes the presence of radicals whose in vivo transport is also controlled by serum albumins. Accordingly, in this study, the interactions between 3-hydroxymethyl-1-oxyl-4-(pyren-1-yl)-2,2,5,5-tetramethyl-2,5-dihydro-1-pyrrole radical and the human serum albumin molecules were investigated.

Alkyl Levulinates and 2-Methyltetrahydrofuran: Possible Biomass-Based Solvents in Palladium-Catalyzed Aminocarbonylation.

In this research, ethyl levulinate, methyl levulinate, and 2-methyltetrahydrofuran as bio-derived hemicellulose-based solvents were applied as green alternatives in palladium-catalyzed aminocarbonylation reactions. Iodobenzene and morpholine were used in optimization reactions under different conditions, such as temperatures, pressures, and ligands. It was shown that the XantPhos ligand had a great influence on conversion (98%) and chemoselectivity (100% carboxamide), compared with the monodentate PPh.

Voltammetric and Fluorimetric Studies of Dibenzoylmethane on Glassy Carbon Electrodes and Its Interaction with Tetrakis (3,5-Dicarboxyphenoxy) Cavitand Derivative.

Due to the medical importance of dibenzoylmethane, one of the aims of the study was to find an appropriate packing material and a biologically friendly co-solvent to help its introduction into living systems. Accordingly, redox properties of dibenzoylmethane were investigated on glassy carbon electrodes in acetonitrile and in 1-propanol with cyclic voltammetry, and showed a diffusion-controlled process. In the anodic window, an oxidation peak appeared at around 1.

Detection of Residual 2-Phenylphenol on Lemon Rind by Electrochemically Deposited Poly(hydroxybenzaldehyde) and Poly(hydroxybenzoic acid) Polymeric Stackings as Electrode Modifiers.

This study explores the characteristics of electrodeposition of the three hydroxybenzaldehyde isomers and selected hydroxybenzoic acids (4-hydroxybenzoic acid, salicylic acid, 3,5-dihydroxybenzoic acid) from mesityl oxide solvent. Similar to recent advances of this solvent, used by electrochemical studies, the carbon-carbon double bond had significant influence on the formation of polymers from the outlined molecules. In case of most substrates the peak currents increased to a steady-state but electropolymerization of some substrates caused significant deactivation.

Anodic Polymerization of Phenylphenols in Methyl Isobutyl Ketone and Mesityl Oxide: Incorporation of a Cavitand into the Layers Formed for Sensing Phenols in Organic Media.

The electropolymerization of three phenylphenol isomers was studied in methyl isobutyl ketone and mesityl oxide, and the remarkable differences highlighted the importance of the carbon-carbon double bond in mesityl oxide. In the case of each substrate, a brownish deposit formed during the electrooxidation. The obvious difference between the polymers formed from the two solvents was recognized via voltammetric signal enhancement of 4-methoxyphenol and 4-chlorophenol, and it was only observed in the case of mesityl oxide.

Measuring volatile emissions from moss gametophytes: A review of methodologies and new applications.

Mosses inhabit nearly all terrestrial ecosystems and engage in important interactions with nitrogen-fixing microbes, sperm-dispersing arthropods, and other plants. It is hypothesized that these interactions could be mediated by biogenic volatile organic compounds (BVOCs). Moss BVOCs may play fundamental roles in influencing local ecologies, such as biosphere-atmosphere-hydrosphere communications, physiological and evolutionary dynamics, plant-microbe interactions, and gametophyte stress physiology.

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation.

Four stereoisomeric monoether derivatives, based on axially chiral ()- or ()-BINOL bearing a chiral (+)- or (-)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)(acac), was attested by P NMR, which presented a doublet in the range of δ = 120 ppm, with a (Rh-P) coupling constant of 290 Hz.

Evaluating the Impact of a Youth-Led Sexual Violence Prevention Program: Youth Leadership Retreat Outcomes.

Involving youth in developing and implementing prevention programs to reduce sexual violence (SV) has the potential to improve prevention outcomes. However, there has been little focus on youth-led SV prevention programs, and limited evaluation research to help guide efforts. The current study examined the effectiveness of Youth Voices in Prevention (Youth VIP) leadership retreats on SV victimization and perpetration, forms of violence related to SV (e.

Automated Insulin Delivery with SGLT2i Combination Therapy in Type 1 Diabetes.

Use of sodium-glucose cotransporter 2 inhibitors (SGLT2i) as adjunct therapy to insulin in type 1 diabetes (T1D) has been previously studied. In this study, we present data from the first free-living trial combining low-dose SGLT2i with commercial automated insulin delivery (AID) or predictive low glucose suspend (PLGS) systems. In an 8-week, randomized, controlled crossover trial, adults with T1D received 5 mg/day empagliflozin (EMPA) or no drug (NOEMPA) as adjunct to insulin therapy.