Bottlebrush Pastes as a Platform for Solvent-Free, Injectable, and Shape-Persistent Materials with Tissue-Mimetic Viscoelasticity.

Architecturally hindered crystallization of bottlebrush graft copolymers offers a reaction- and solvent-free pathway for creating injectable elastomers with tissue-mimetic softness. Currently, injectable materials involve solvents and chemical reactions, leading to uncontrolled swelling, leaching of unreacted moieties, and side reactions with tissue. To address this issue, bottlebrush copolymers with a poly(ethylene glycol) (PEG) amorphous block and crystallizable poly(lactic acid) (PLA) grafted chains (A--B) were synthesized, with grafted chains of controlled length arranged along the backbone at controlled spacing.

Self-Diffusion of Star and Linear Polyelectrolytes in Salt-Free and Salt Solutions.

This work explored solution properties of linear and star poly(methacrylic acids) with four, six, and eight arms (PMAA, 4PMAA, PMAA, and 8PMAA, respectively) of matched molecular weights in a wide range of pH, salt, and polymer concentrations. Experimental measurements of self-diffusion were performed by fluorescence correlation spectroscopy (FCS), and the results were interpreted using the scaling theory of polyelectrolyte solutions. While all PMAAs were pH sensitive and showed an increase in hydrodynamic radius ( ) with pH in the dilute regime, the of star polymers (measured at basic pH values) was significantly smaller for the star polyacids due to their more compact structure.

Enhancing the Biomimetic Mechanics of Bottlebrush Graft-Copolymers through Selective Solvent Annealing.

Self-assembled networks of bottlebrush copolymers are promising materials for biomedical applications due to a unique combination of ultra-softness and strain-adaptive stiffening, characteristic of soft biological tissues. Transitioning from ABA linear-brush-linear triblock copolymers to A-g-B bottlebrush graft copolymer architectures allows significant increasing the mechanical strength of thermoplastic elastomers. Using real-time synchrotron small-angle X-ray scattering, it is shown that annealing of A-g-B elastomers in a selective solvent for the linear A blocks allows for substantial network reconfiguration, resulting in an increase of both the A domain size and the distance between the domains.

[Artificial ventilation in patients with stroke: main results of the Russian multicenter observational clinical trial RETAS].

Objective: To analyze the relationship between the characteristics of respiratory support (RS) for patients with stroke and clinical factors with the number and structure of complications, deaths, and length of stay in the intensive care unit (ICU) and duration of artificial pulmonary ventilation (ALV).

Material And Methods: The Russian multicenter observational clinical study «Respiratory Therapy for Acute Stroke» (RETAS) that enrolled 1289 patients with stroke requiring RS was conducted under the auspices of the All-Russian public organization «Federation of Anesthesiologists and Resuscitators». Indications for ALV, the use of hyperventilation, the maximum level of positive end-expiratory pressure, starting modes of mechanical ventilation, timing of tracheostomy, the incidence of protein-energy malnutrition (PEM) and infectious complications were analyzed.

When the Poisson Ratio of Polymer Networks and Gels Is Larger Than 0.5?

We use coarse-grained molecular dynamics simulations to study deformation of networks and gels of linear and brush strands in both linear and nonlinear deformation regimes under constant pressure conditions. The simulations show that the Poisson ratio of networks and gels could exceed 0.5 in the nonlinear deformation regime.

Design of luminescent complexes with different CuI cores based on pyridyl phenoxarsines.

A series of luminescent CuI clusters with stair-step, cubane, and octahedral geometries supported by a novel type of cyclic As,N-ligand, pyridyl-containing 10-phenoxarsines, were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. An unusual arrangement of As,N-bidentate and μ-iodo ligands was found in the octahedral cluster. The structural diversity of the Cu(I) complexes is reflected in their photophysical properties: the phosphorescence spectra of the compounds display emission in a broad spectral range of 495-597 nm.

An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH-Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants.

We report an unusual transformation where the transient formation of a nitrene moiety initiates a sequence of steps leading to remote oxidative C-H functionalization (R-CH to R-CHOC(O)R') and the concomitant reduction of the nitrene into an amino group. No external oxidants or reductants are needed for this formal molecular comproportionation. Detected and isolated intermediates and computational analysis suggest that the process occurs with pyrazole ring opening and recyclization.

Resorbable barrier polymers for flexible bioelectronics.

Resorbable, implantable bioelectronic devices are emerging as powerful tools to reliably monitor critical physiological parameters in real time over extended periods. While degradable magnesium-based electronics have pioneered this effort, relatively short functional lifetimes have slowed clinical translation. Barrier films that are both flexible and resorbable over predictable timelines would enable tunability in device lifetime and expand the viability of these devices.

Coarse-Grained Artificial Intelligence for Design of Brush Networks.

The ability to synthesize elastomeric materials with programmable mechanical properties is vital for advanced soft matter applications. Due to the inherent complexity of hierarchical structure-property correlations in brush-like polymer networks, the application of conventional theory-based, so-called Human Intelligence (HI) approaches becomes increasingly difficult. Herein we developed a design strategy based on synergistic combination of HI and AI tools which allows precise encoding of mechanical properties with three architectural parameters: degrees of polymerization (DP) of network strands, , side chains, , backbone spacers between side chains, .

Forensics of polymer networks.

Our lives cannot be imagined without polymer networks, which range widely, from synthetic rubber to biological tissues. Their properties-elasticity, strain-stiffening and stretchability-are controlled by a convolution of chemical composition, strand conformation and network topology. Yet, since the discovery of rubber vulcanization by Charles Goodyear in 1839, the internal organization of networks has remained a sealed 'black box'.

Bottlebrush Thermoplastic Elastomers as Hot-Melt Pressure-Sensitive Adhesives.

Hot-melt pressure-sensitive adhesives (HMPSAs) are used in applications from office supplies to biomedical adhesives. The major component in HMPSA formulations is thermoplastic elastomers, such as styrene-based block copolymers, that provide both mechanical integrity and moldability. Since neat polymer networks are unable to establish an adhesive bond, large quantities of plasticizers and tackifiers are added.

Mechanochromism and Strain-Induced Crystallization in Thiol-yne-Derived Stereoelastomers.

Most elastomers undergo strain-induced crystallization (SIC) under tension; as individual chains are held rigidly in a fixed position by an applied strain, their alignment along the strain field results in a shift from strain-hardening (SH) to SIC. A similar degree of stretching is associated with the tension necessary to accelerate mechanically coupled, covalent chemical responses of mechanophores in overstretched chains, raising the possibility of an interplay between the macroscopic response of SIC and the molecular response of mechanophore activation. Here, thiol-yne-derived stereoelastomers doped covalently with a dipropiolate-derivatized spiropyran (SP) mechanophore (0.

Synthesis and Anticancer Evaluation of Novel 7-Aza-Coumarine-3-Carboxamides.

Herein, we report the design and synthesis of novel 7-aza-coumarine-3-carboxamides via scaffold-hopping strategy and evaluation of their in vitro anticancer activity. Additionally, the improved non-catalytic synthesis of 7-azacoumarin-3-carboxylic acid is reported, which features water as the reaction medium and provides a convenient alternative to the known methods. The anticancer activity of the most potent 7-aza-coumarine-3-carboxamides against the HuTu 80 cell line is equal to that of reference Doxorubicin, while the selectivity towards the normal cell line is 9-14 fold higher.

Viscosity of Polymer Solutions and Molecular Weight Characterization.

Since the pioneering research by Staudinger on dilute solution viscosity and its relation to the polymer molecular weight, viscosity analysis has become a valuable technique for polymer characterization. The conventional approach is based on the Huggins approximation of the solution-specific viscosity by a quadratic function of concentration, . We show how to reformulate this approach in a universal form by representing a solution-specific viscosity, η, as a generalized universal function η(c) = α(/*) + (1 - α)(/*) of chain overlap concentration, *, determined at η = 1, with numerical coefficients α = 0.

Covalent Functionalization of Black Phosphorus Nanosheets with Dichlorocarbenes for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

Two-dimensional black phosphorus (BP) has emerged as a perspective material for various micro- and opto-electronic, energy, catalytic, and biomedical applications. Chemical functionalization of black phosphorus nanosheets (BPNS) is an important pathway for the preparation of materials with improved ambient stability and enhanced physical properties. Currently, the covalent functionalization of BPNS with highly reactive intermediates, such as carbon-free radicals or nitrenes, has been widely implemented to modify the material's surface.

Sticky Architecture: Encoding Pressure Sensitive Adhesion in Polymer Networks.

Pressure sensitive adhesives (PSAs) are ubiquitous materials within a spectrum that span from office supplies to biomedical devices. Currently, the ability of PSAs to meet the needs of these diverse applications relies on trial-and-error mixing of assorted chemicals and polymers, which inherently entails property imprecision and variance over time due to component migration and leaching. Herein, we develop a precise additive-free PSA design platform that predictably leverages polymer network architecture to empower comprehensive control over adhesive performance.

Self-consistent computation of spin torques and magneto-resistance in tunnel junctions and magnetic read-heads with metallic pinhole defects.

A three-dimensional self-consistent spin transport model is developed, which includes both tunnelling transport, leading to tunnelling magneto-resistance, as well as metallic transport, leading to giant magneto-resistance. An explicit solution to the drift-diffusion model is also derived, which allows analysing the effect of both the reference and free layer thickness on the spin-transfer torque polarization and field-like coefficient. It is shown the model developed here can be used to compute the signal-to-noise ratio in realistic magnetic read-heads, where spin torque-induced fluctuations and instabilities limit the maximum operating voltage.

Water-Soluble Salts Based on Benzofuroxan Derivatives-Synthesis and Biological Activity.

A series of novel water-soluble salts of benzofuroxans was achieved via aromatic nucleophilic substitution reaction of 4,6-dichloro-5-nitrobenzofuroxan with various amines. The salts obtained showed good effectiveness of the pre-sowing treatment of seeds of agricultural crops at concentrations of 20-40 mmol. In some cases, the seed treatment with salts leads not only to improved seed germination, but also to the suppression of microflora growth.

PNP Ligands in Cobalt-Mediated Activation and Functionalization of White Phosphorus.

Transition-metal mediated white phosphorus activation is of high interest as an ecological alternative to P chlorination pathway to the practically useful phosphorus products. Herein, we report a facile approach for P activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands. The use of N,N-bis(diphenylphosphino)amine as a ligand allows one to transform P tetrahedron into a zig-zag chain with the formation of complex [Co(Ph PNHP(Ph )PPPPP(Ph )NHPPh )]BF (4).

Super-soft, firm, and strong elastomers toward replication of tissue viscoelastic response.

Polymeric networks are commonly used for various biomedical applications, from reconstructive surgery to wearable electronics. Some materials may be soft, firm, strong, or damping however, implementing all four properties into a single material to replicate the mechanical properties of tissue has been inaccessible. Herein, we present the A--B brush-like graft copolymer platform as a framework for fabrication of materials with independently tunable softness and firmness, capable of reaching a strength of ∼10 MPa on par with stress-supporting tissues such as blood vessel, muscle, and skin.

Diastereoselective intramolecular cyclization/Povarov reaction cascade for the one-pot synthesis of polycyclic quinolines.

The method for the synthesis of complex alkaloid-like aza-heterocycles has been developed through the Povarov reaction of generated 2-oxoimidazolium cations. The reaction lead to the formation of 2 C-N, 2 C-C bonds and three stereocentres, and features excellent regio- and diastereoselectivity. Based on the controlled experiments and quantum chemistry data, the mechanism of the reaction cyclization was proposed and diastereoselectivity origins were rationalized.

Mechanically Diverse Gels with Equal Solvent Content.

Mechanically diverse polymer gels are commonly integrated into biomedical devices, soft robots, and tissue engineering scaffolds to perform distinct yet coordinated functions in wet environments. Such multigel systems are prone to volume fluctuations and shape distortions due to differential swelling driven by osmotic solvent redistribution. Living systems evade these issues by varying proximal tissue stiffness at nearly equal water concentration.

Ultra-Tough Elastomers from Stereochemistry-Directed Hydrogen Bonding in Isosorbide-Based Polymers.

The remarkable elasticity and tensile strength found in natural elastomers are challenging to mimic. Synthetic elastomers typically feature covalently cross-linked networks (rubbers), but this hinders their reprocessability. Physical cross-linking via hydrogen bonding or ordered crystallite domains can afford reprocessable elastomers, but often at the cost of performance.

Sugar-Based Polymers with Stereochemistry-Dependent Degradability and Mechanical Properties.

Stereochemistry in polymers can be used as an effective tool to control the mechanical and physical properties of the resulting materials. Typically, though, in synthetic polymers, differences among polymer stereoisomers leads to incremental property variation, i.e.