Water training initiates spatially regulated microstructures with competitive mechanics in hydroadaptive polymers.

The strategy using water as a medium for dynamic modulation of competitive plasticity and viscoelasticity provides a unique perspective to attain adaptive materials. We reveal sustainable polymers, herein cellulose phenoxyacetate as a typical example, with unusual water-responsive dual-mechanic functionalities addressed via a chronological water training strategy. The temporal significance of such water-responsive mechanical behaviors becomes apparent considering that a mere 3-minute exposure or a prolonged 3-hour exposure to water induced different types of mechano-responsiveness.

Viscoelastic Response in Hydrous Polymers: The Role of Hydrogen Bonds and Microstructure.

Water responsive polymers represent a remarkable group of soft materials, acting as a laboratory for diverse water responsive physical phenomena and cutting-edge biology-electronics interfaces. We report on peculiarly distinctive viscoelastic behaviors of the biobased water responsive polymer cellulose 10-undecenoyl ester, while biobased regenerated cellulose displays stronger hydroplastic behaviors. We discovered a novel hydrous deformation mechanism involving the stretching of hydrogen bonds mediated by hydroxyl groups and water molecules, serving as a crucial factor in accommodating deformations.

Scale-Spanning Strong Adhesion Using Cellulose-Based Microgels.

Adhesive gels derived from biobased sustainable materials have extremely broad application prospects, such as in flexible smart materials and biomedicine fields. Combining high toughness and strong, persisting repeatable adhesion has always been a daunting challenge for adhesive gels. However, bulk gels based on polysaccharides as the most abundant bio-based compounds usually possess a high toughness but weak interfacial adhesion due to the strong hydration potential.

Block Copolymers Featuring Highly Photostable Photoacids Based on Vinylnaphthol: Synthesis and Self-Assembly.

The synthesis of a photoresponsive amphiphilic diblock quarterpolymer containing 5-vinyl-1-naphthol (VN) as a photostable photoacidic comonomer is presented. The preparation is realized via a sequential reversible addition fragmentation chain transfer (RAFT) polymerization starting from a nona(ethylene glycol) methyl ether methacrylate (MEO MA/"O") hydrophilic block, which is then used as a macro-RAFT agent in the terpolymerization of styrene (S), 2-vinylpyridine (2VP), and TBS-protected VN (tVN). The terpolymerization proceeds in a controlled fashion and two diblock quarterpolymers, P(O )-b-P(S -co-2VP -co-VN ), with varying functional comonomer compositions are prepared.

pH-Responsive Side Chains as a Tool to Control Aqueous Self-Assembly Mechanisms.

pH-Tunable nanoscale morphology and self-assembly mechanism of a series of oligo(p-phenyleneethynylene) (OPE)-based bolaamphiphiles featuring poly(ethylene imine) (PEI) side chains of different length and degree of hydrolysis are described. Protonation and deprotonation of the PEI chains by changing the pH alters the hydrophilic/hydrophobic balance of the systems and, in turn, the strength of intermolecular interactions between the hydrophobic OPE moieties. Low pH values (3) lead to weak interaction between the OPEs and result in spherical nanoparticles, in which aggregation follows an isodesmic mechanism.

Tackling the Limitations of Copolymeric Small Interfering RNA Delivery Agents by a Combined Experimental-Computational Approach.

Despite the first successful applications of nonviral delivery vectors for small interfering RNA in the treatment of illnesses, such as the respiratory syncytial virus infection, the preparation of a clinically suitable, safe, and efficient delivery system still remains a challenge. In this study, we tackle the drawbacks of the existing systems by a combined experimental-computational in-depth investigation of the influence of the polymer architecture over the binding and transfection efficiency. For that purpose, a library of diblock copolymers with a molar mass of 30 kDa and a narrow dispersity (Đ < 1.

Different Routes to Ampholytic Polydehydroalanine: Orthogonal versus Simultaneous Deprotection.

Polydehydroalanine (PDha) is a polyampholyte featuring both a -NH and a -COOH in every repeat unit and with that presents a rather high charge density. The synthesis and polymerization of two monomers, benzyl 2-tert-butoxycarbonylaminoacrylate and methyl 2-benzyloxycarbonylaminoacrylate is herein reported, which feature different protective groups and, after polymerization, the resulting PtBABA and PBOMA can be transformed into PDha using polymer-analogous modification reactions. More important, the current choice of protective groups allows either simultaneous deprotection in one step in both cases, but also the orthogonal deprotection of either -NH or -COOH moiety for PtBABA, given that appropriate conditions are chosen.

Controlling the Miscibility of X-Shaped Bolapolyphiles in Lipid Membranes by Varying the Chemical Structure and Size of the Polyphile Polar Headgroup.

Bolaamphiphiles are well-known naturally occurring structures that can increase the thermal and mechanical stability of the phospholipid membrane by incorporation in a transmembrane manner. Modifications of bolaamphiphiles to introduce particular structural elements such as a conjugated aromatic backbone and lateral side chains in the hydrophobic region lead to bolapolyphiles (BPs). We investigated the ability of BPs to form lyotropic phases in water.

Reversible Adsorption of Methylene Blue as Cationic Model Cargo onto Polyzwitterionic Magnetic Nanoparticles.

The reversible electrostatic adsorption of the cationic dye methylene blue (MB) as a model compound to polydehydroalanine (PDha)-coated magnetic multicore nanoparticles (MCNP) is presented. The pH responsiveness of the zwitterionic coating material enables reversible switching of the net surface charge of the PDha@MCNP hybrid particles by changes in pH and thus allows reversible adsorption of MB at neutral pH and desorption at low pH values. The resulting hybrid materials can be very interesting systems in the context of water purification, and the reversible adsorption is studied using UV-vis spectroscopy under varying surrounding conditions.

Synthesis, Characterization, and Applications of Magnetic Nanoparticles Featuring Polyzwitterionic Coatings.

Throughout the last decades, magnetic nanoparticles (MNP) have gained tremendous interest in different fields of applications like biomedicine (e.g., magnetic resonance imaging (MRI), drug delivery, hyperthermia), but also more technical applications (e.

Zwitterionic Iron Oxide (γ-Fe O ) Nanoparticles Based on P(2VP-grad-AA) Copolymers.

This study presents the synthesis and characterization of zwitterionic core-shell hybrid nanoparticles consisting of a core of iron oxide multicore nanoparticles (MCNPs, γ-Fe O ) and a shell of sultonated poly(2-vinylpyridine-grad-acrylic acid) copolymers. The gradient copolymers are prepared by reversible addition fragmentation chain transfer polymerization of 2-vinylpyridine (2VP), followed by the addition of tert-butyl acrylate and subsequent hydrolysis. Grafting of P(2VP-grad-AA) onto MCNP results in P(2VP-grad-AA)@MCNP, followed by quaternization using 1,3-propanesultone-leading to P(2VP -grad-AA)@MCNP with a zwitterionic shell.