Tailoring a Dress to Single Protein Molecules: Proteins Can Do It Themselves through Localized Photo-Polymerization and Molecular Imprinting

Molecularly imprinted polymer nanoparticles (MIP NPs) are antibody-like recognition materials prepared by a template-assisted synthesis. MIP NPs able to target biomolecules, like proteins, are under the spotlight for their great potential in medicine, but efficiently imprinting biological templates is still very challenging. Here we propose generating a molecular imprint in single NPs, by photochemically initiating the polymerization from individual protein templates. In this way, each protein molecule tailors itself its own “polymeric dress”. For this, the template protein is covalently coupled with a photoinitiator, Eosin Y. Irradiated with light at 533 nm, the Eosin moiety acts as an antenna and transfers energy to a co-initiator (an amine), which generates a radical and initiates polymerization. As a result, a polymer network is forming only around the very template molecule, producing cross-linked NPs of 50 nm, with single binding sites showing high affinity (K_D 10⁻⁹ m ) for their biological target, and selectivity over other proteins.     

Modulation of Mechanical Interactions by Local Piezoelectric Effects

Piezoelectricity is a well‐established property of biological materials, yet its functional role has remained unclear. Here, a mechanical effect of piezoelectric domains resulting from collagen fibril organisation is demonstrated, and its role in tissue function and application to material design is described. Using a combination of scanning probe and nonlinear optical microscopy, a hierarchical structuring of piezoelectric domains in collagen‐rich tissues is observed, and their mechanical effects are explored in silico. Local electrostatic attraction and repulsion due to shear piezoelectricity in these domains modulate fibril interactions from the tens of nanometre (single fibril interactions) to the tens of micron (fibre interactions) level, analogous to modulated friction effects. The manipulation of domain size and organisation thus provides a capacity to tune energy storage, dissipation, stiffness, and damage resistance.     

Binary Cellulose Nanocrystal Blends for Bioinspired Damage Tolerant Photonic Films

Most attempts to emulate the mechanical properties of strong and tough natural composites using helicoidal films of wood‐derived cellulose nanocrystals (w‐CNCs) fall short in mechanical performance due to the limited shear transfer ability between the w‐CNCs. This shortcoming is ascribed to the small w‐CNC‐w‐CNC overlap lengths that lower the shear transfer efficiency. Herein, we present a simple strategy to fabricate superior helicoidal CNC films with mechanical properties that rival those of the best natural materials and are some of the best reported for photonic CNC materials thus far. Assembling the short w‐CNCs with a minority fraction of high aspect ratio CNCs derived from tunicates (t‐CNCs), we report remarkable simultaneous enhancement of all in‐plane mechanical properties and out‐of‐plane flexibility. The important role of t‐CNCs is revealed by coarse grained molecular dynamics simulations where the property enhancement are due to increased interaction lengths and the activation of additional toughening mechanisms. At t‐CNC contents greater than 5% by mass the mixed films also display UV reflecting behaviour. These damage tolerant optically active materials hold great promise for application as protective coatings. More broadly, we expect the strategy of using length‐bidispersity to be adaptable to mechanically enhancing other matrix‐free nanoparticle ensembles.     

Biomimicry of Social Foraging Bacteria for Distributed Optimization: Models,Principles, and Emergent Behaviors

In this paper, we explain the social foraging behavior of E. coli and M. xanthus bacteria and develop simulation models based on the principles of foraging theory that view foraging as optimization. This provides us with novel models of their foraging behavior and with new methods for distributed nongradient optimization. Moreover, we show that the models of both species of bacteria exhibit the property identified by Grunbaum that postulates that their foraging is social in order to be able to climb noisy gradients in nutrients. This provides a connection between evolutionary forces in social foraging and distributed nongradient optimization algorithm design for global optimization over noisy surfaces.     

Biomimetic 4D-Printed Breathing Hydrogel Actuators by Nanothylakoid and Thermoresponsive Polymer Networks

Shape-morphing actuators, which can breathe with the accompany of morphology changes to mimic botanical events, are challenging to fabricate with soft hydrogel materials. Herein, 4D printed-smart hydrogel actuators are reported that can not only dynamically deform but also generate oxygen (O₂) upon external stimulations. The printed breathing actuators featured with spinach leaf-derived thylakoid membrane (nanothylakoid) for photothermal conversion and catalytical O₂ evolution, a poly(N-isopropylacrylamide) (PNIPA) thermoresponsive polymer network for generating deformation forces by swelling/shrinkage (rehydration/dehydration), and an asymmetric bilayer poly(N-isopropylacrylamide)/polyacrylamide (PNIPA/PAA) structure to amplify the mechanical motions. Upon thermal stimulation or laser irradiation, the actuator can reversibly bend/unbend because of the photothermal conversion of nanothylakoid and the printed thermoresponsive asymmetric bilayer structure. Additionally, the catalase-like property of nanothylakoid imparts the actuator with O₂ evolution capability to breathe for further mimicking botanical systems. Notably, 4D printing can greatly facilitate and simplify the actuator fabrication process, including adjusting the size and layer compositions. This artificial breathing actuator with photothermal and catalytical properties provides a strategy in designing intelligent hydrogel systems and proves to be a highly promising material candidates in the fields of 3D/4D printing, automated robotics, and smart biomedical devices.     

Synthesis of “bioinspired” copolymers: experimental and theoretical investigation on poly(vinyl benzyl thymine-co-triethyl ammonium chloride)

Abstract

“Bioinspired” copolymers based on vinylbenzyl thymine (VBT) and an ionically-charged monomer, such as vinylbenzyl triethylammonium chloride (VBA), were synthesized and theoretically investigated. These water-soluble copolymers are polystyrene- (PS) based, and their structure mimics DNA. In the presence of short-wavelength UV light, the thymine groups dimerize into non-toxic, environmentally benign, and biodegradable photo-resistant materials. Copolymerizations with different comonomer ratios were carried out at 65°C. Samples were taken along the reactions to determine monomer conversion, chemical composition, and molecular weight distribution. While average molecular weights fall along the reaction, the average composition remains almost constant and coincident with the initial comonomer ratios, thus indicating a similar reactivity of all the comonomer radicals. A mathematical model was developed that simulates the synthesis of the base biopolymer, in the sense of predicting the evolution of the global reaction variables and molecular structure of the polymer. The termination and propagation kinetic constants were adjusted to the experimental data. The resulting values are quite different to those of a normal styrene homopolymerization, thus suggesting a noticeable effect of the solvent and the comonomer pending groups.     

Polypyrrole Asymmetric Bilayer Artificial Muscle: Driven Reactions,Cooperative Actuation,and Osmotic Effects

The coulo‐dynamic (angle/consumed charge) characterization of an asymmetric polypyrrole (PPy) bending bilayer (PPy₁/PPy₂) muscle is performed in aqueous solutions by cyclic voltammetry with parallel video recording of a reversible angular displacement of 200°. The characterization of each of the two PPy₁/tape, PPy₂/tape muscles, describing 30° and 50° per voltammetric cycle, corroborates the driven muscle reactions and ionic exchanges. The asymmetric bilayer efficiency, as described degrees per reaction unit, is seven and four times that of the PPy/tape muscles. A cooperative electro‐chemo‐mechanical actuation of each of the individual layers occurs in the asymmetric bilayer. Each of the three muscles is a Faradaic polymeric motor: described angles are linear functions of the consumed charge with small hysteresis loops. Each loop is related to dynamic water osmotic balance following the reaction driven film swelling or its fast electro‐osmotic expulsion around the reduction induced conformational closing and film compaction.