Exploiting thiol-functionalized benzosiloxaboroles for achieving diverse substitution patterns - synthesis, characterization and biological evaluation of promising antibacterial agents.

Benzosiloxaboroles are an emerging class of medicinal agents possessing promising antimicrobial activity. Herein, the expedient synthesis of two novel thiol-functionalized benzosiloxaboroles 1e and 2e is reported. The presence of the SH group allowed for diverse structural modifications involving the thiol-Michael addition, oxidation, as well as nucleophilic substitution giving rise to a series of 27 new benzosiloxaboroles containing various polar functional groups, , carbonyl, ester, amide, imide, nitrile, sulfonyl and sulfonamide, and pendant heterocyclic rings.

Fluorophilic Sigma(σ)-Lock Self-Healable Copolymers.

Although F-Containing molecules and macromolecules are often used in molecular biology to increase the binding with Lewis acidic groups by introducing favorable C-F dipoles, there is virtually no experimental evidence and limited understanding of the nature of these interactions, especially their role in synthetic polymeric materials. These studies elucidate the molecular origin of inter- and intra-Chain interactions responsible for self-healing of F-Containing copolymers composed of pentafluorostyrene and n-butyl acrylate units (p(PFS/nBA). Guided by dynamic surface oscillating force (SOF) and spectroscopic measurements supported by molecular dynamics (MD) simulations, these studies show that the reformation of σ-σ orbitals in -C-F of PFS and CHCH- of nBA units enables the recovery of entropic energy via fluorophilic-σ-lock van der Waals forces when PFS/nBA molar ratios are ~50/50.

Dynamic Interfaces in Self-Healable Polymers.

It is well-established that interfaces play critical roles in biological and synthetic processes. Aside from significant practical applications, the most accessible and measurable quantity is interfacial tension, which represents a measure of the energy required to create or rejoin two surfaces. Owing to the fact that interfacial processes are critical in polymeric materials, this review outlines recent advances in dynamic interfacial processes involving physics and chemistry targeting self-healing.

Highly electron-deficient 3,6-diaza-9-borafluorene scaffolds for the construction of luminescent chelate complexes.

The synthesis and characterization of two fluorinated 3,6-diaza-9-hydroxy-9-borafluorene oxonium acids featuring improved hydrolytic stability and the strong electron-deficient character of the diazaborafluorene core is reported. These boracycles served as precursors of fluorescent spiro-type complexes with (O,N)-chelating ligands which revealed specific properties such as delayed emission, white light emission in the solid state and photocatalytic performance in singlet oxygen-mediated oxidation reactions.

Democratic Spirit, Emotions, Help, and Hope during the Russian war against Ukraine: Experience from the Czech Republic.

This study is based on an original eight-wave longitudinal survey conducted in the Czech Republic (N = 1622, national quota sample). Structural equation modeling (SEM) was employed to create a mediation model to test whether democratic spirit assessed in March 2021 (1 year before the Russian invasion) predicted responses to the major crisis (measured immediately, 2 months, and 9 months after the invasion). The Russian invasion of February 2022 deeply impacted Czech democrats.

Bis[1]benzothieno[1,4]thiaborins as a Platform for BODIPY Singlet Oxygen Photosensitizers.

Invited for the cover of this issue are Krzysztof Durka and co-workers at Warsaw University of Technology, University of Warsaw, Silesian University of Technology and Heinrich-Heine-Universität. The image depicts the generation of singlet oxygen by the BODIPY photosensitizer. Read the full text of the article at 10.

Interactions in Self-Healable Styrenic Copolymers.

Commodity copolymers offer many useful applications, and their durability is critical in maintaining desired functions and retaining sustainability. These studies show that primarily alternating styrene/-butyl acrylate [p(Sty/BA)] copolymers self-heal without external intervention when monomer molar ratios are within the 45:55-53:47 range. This behavior is attributed to the favorable interchain interactions between aliphatic nBA side groups being sandwiched by aromatic rings forming associations driven by pi-sigma-pi (π-σ-π) interactions.

Bis[1]benzothieno[1,4]thiaborins as a Platform for BODIPY Singlet Oxygen Photosensitizers.

A synthetic approach to two regioisomeric π-electron extended [1,4]thiaborins annulated with two benzothiophene units has been developed. The central thiaborin rings of the boracycles obtained exhibit different electronic properties; this is reflected in their different aromatic characters, boron Lewis acidity and UV-vis spectroscopic behavior. Thiaborins were converted to boron dipyrromethene (BODIPY) complexes.

Parental Interference in Offspring's Mate Choice: Sets of Actions and Counteractions Based on Both Perspectives.

Mate choice in humans is specific by the involvement of kin both in partner choice and in the functioning of the relationship. The influence of relatives ranges from providing advice all the way to arranged marriages. Existing research so far tended to map neither the actual parental interventions and further reactions (counteractions) nor the independently pursued behavior (actions) by which the offspring or their partners assert their interests.

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor-Acceptor Emitter Featuring a Hybrid Sulfone-Triarylboron Acceptor.

10H-Dibenzo[b,e][1,4]thiaborinine 5,5-dioxide (SO2B)-a high triplet (T =3.05 eV) strongly electron-accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ-Dipp-SO2B and CZ-Dipp-SO2B. We demonstrate the near-complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S →S CT transition, resulting in very long ca.

Oxazoline scaffold in synthesis of benzosiloxaboroles and related ring-expanded heterocycles: diverse reactivity, structural peculiarities and antimicrobial activity.

Two isomeric benzosiloxaborole derivatives 3a and 5a bearing fluorine and 4,4-dimethyl-2-oxazolin-2-yl substituents attached to the aromatic rings were obtained. Both compounds were prone to hydrolytic cleavage of the oxazoline ring after initial protonation or methylation of the nitrogen atom. The derivative 3c featuring -methylammoniumalkyl ester functionality was successfully subjected to -sulfonylation and -acylation reactions to give respective derivatives which demonstrates its potential for modular synthesis of structurally extended benzosiloxaboroles.

Electrically Accelerated Self-Healable Polyionic Liquid Copolymers.

Electrically accelerated self-healable poly(ionic liquids) copolymers that exhibit resistor-capacitor (RC) circuit properties are developed. At low alternating current (AC) frequencies these materials behave as a resistor (R), whereas at higher frequencies as a capacitor (C). These properties are attributed to a combination of dipolar and electrostatic interactions in (1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethyl-sulfonyl)imide) copolymerized with methyl methacrylate (MMA) monomers to form p(MEBIm-TSFI/MMA)] copolymers.

Heavy-Atom Free Organoboron Complexes As Triplet Excited States Photosensitizers for Singlet Oxygen Activation.

Herein, we present a new strategy for the development of efficient heavy-atom free singlet oxygen photosensitizers based on rigid borafluorene scaffolds. Physicochemical properties of borafluorene complexes can be easily tuned through the choice of ligand, thus allowing exploration of numerous organoboron structures as potent O sensitizers. The singlet oxygen generation quantum yields of studied complexes vary in the range of 0.

Self-Healable Fluorinated Copolymers Governed by Dipolar Interactions.

Although dipolar forces between copolymer chains are relatively weak, they result in ubiquitous inter- and/or intramolecular interactions which are particularly critical in achieving the mechanical integrity of polymeric materials. In this study, a route is developed to obtain self-healable properties in thermoplastic copolymers that rely on noncovalent dipolar interactions present in essentially all macromolecules and particularly fluorine-containing copolymers. The combination of dipolar interactions between C─F and C═O bonds as well as CH /CH entities facilitates self-healing without external intervention.

Recent Advances in Stimuli-Responsive Commodity Polymers.

Known for their adaptability to surroundings, capability of transport control of molecules, or the ability of converting one type of energy to another as a result of external or internal stimuli, responsive polymers play a significant role in advancing scientific discoveries that may lead to an array of diverge applications. This review outlines recent advances in the developments of selected commodity polymers equipped with stimuli-responsiveness to temperature, pH, ionic strength, enzyme or glucose levels, carbon dioxide, water, redox agents, electromagnetic radiation, or electric and magnetic fields. Utilized diverse applications ranging from drug delivery to biosensing, dynamic structural components to color-changing coatings, this review focuses on commodity acrylics, epoxies, esters, carbonates, urethanes, and siloxane-based polymers containing responsive elements built into their architecture.

Anchoring Effect of Performance Feedback on Accuracy of Metacognitive Monitoring in Preschool Children.

Preschool children are generally inaccurate at evaluating past and predicting future performance. The present study examines the effect of performance feedback on the accuracy of preschoolers' predictive judgments and tests whether performance feedback acts as an anchor for postdictive judgments. In Experiment 1, preschool children (n = 40) solved number patterns, and in Experiment 2 they solved object patterns (n = 59).

Water accelerated self-healing of hydrophobic copolymers.

Previous studies have shown that copolymer compositions can significantly impact self-healing properties. This was accomplished by enhancement of van der Waals (vdW) forces which facilitate self-healing in relatively narrow copolymer compositional range. In this work we report the acceleration of self-healing in alternating/random hydrophobic acrylic-based copolymers in the presence of confined water molecules.

Entropy and interfacial energy driven self-healable polymers.

Although significant advances have been achieved in dynamic reversible covalent and non-covalent bonding chemistries for self-healing polymers, an ultimate goal is to create high strength and stiffness commodity materials capable of repair without intervention under ambient conditions. Here we report the development of mechanically robust thermoplastic polyurethane fibers and films capable of autonomous self-healing under ambient conditions. Two mechanisms of self-healing are identified: viscoelastic shape memory (VESM) driven by conformational entropic energy stored during mechanical damage, and surface energy/tension that drives the reduction of newly generated surface areas created upon damage by shallowing and widening wounds until healed.

Mechanistic Insights on Spontaneous Moisture-Driven Healing of Urea-Based Polyurethanes.

Self-healing polymeric materials that can spontaneously repair in a perpetual manner are highly appealing to address safety and restoration issues in different key applications. Usually built from reversible moieties that require to be activated using, for example, temperature, light, or pH changes, most of these self-healing materials rely on energy-demanding processes and/or external interventions to promote self-healing. In this work, we propose to exploit rapid dynamic exchanges between urea-based moieties and moisture as an alternative to promote local and spontaneous healing responses to damage using atmospheric moisture as an external stimulus.

Key-and-lock commodity self-healing copolymers.

Self-healing materials are notable for their ability to recover from physical or chemical damage. We report that commodity copolymers, such as poly(methyl methacrylate)/n-butyl acrylate [p(MMA/nBA)] and their derivatives, can self-heal upon mechanical damage. This behavior occurs in a narrow compositional range for copolymer topologies that are preferentially alternating with a random component (alternating/random) and is attributed to favorable interchain van der Waals forces forming key-and-lock interchain junctions.

Stimuli-Responsive Polymeric Nanoparticles.

There is increasing evidence that stimuli-responsive nanomaterials have become significantly critical components of modern materials design and technological developments. Recent advances in synthesis and fabrication of stimuli-responsive polymeric nanoparticles with built-in stimuli-responsive components (Part A) and surface modifications of functional nanoparticles that facilitate responsiveness (Part B) are outlined here. The synthesis and construction of stimuli-responsive spherical, core-shell, concentric, hollow, Janus, gibbous/inverse gibbous, and cocklebur morphologies are discussed in Part A, with the focus on shape, color, or size changes resulting from external stimuli.

Quantitative Predictions of Shape-Memory Effects in Polymers.

Unique shape-memory transitions manifested by directional extension and subsequent retraction in polymers are attributed to stored conformational entropy. This behavior is quantified in terms of stored (ΔS ) entropic energy density, the maximum strain (ε ), and stress (σ at ε ). This concept allows quantitative assessments of the shape-memory effect (SME) and can be utilized in any material that exhibits a glass-transition temperature (T ) and a rubbery plateau.