Temperature-responsive bioactive glass/polymer hybrids allow for tailoring of ion release.

Intelligent biomaterials react to their surrounding conditions, and hybrid materials are acknowledged for their remarkable customizability, achieved through the meticulous control of nanoscale interactions between organic and inorganic phases. Bioactive glasses (BG) are used clinically to regenerate bone due to their degradability, ion release, and capacity to stimulate the formation of new body tissue. In our study, we developed a core-shell hybrid system using sol-gel derived BG nano particles as the core and poly (N-isopropyl acrylamide) (PNIPAM) as the shell. This approach aims to combine the therapeutic ion release of BG with the temperature-responsive properties of PNIPAM. Our size analysis by dynamic light scattering at varying temperatures shows the formation of BG aggregates driven by the coil-to-globule transition of PNIPAM on the BG surface. This transition also affected the ion release from the core-shell system through an increase in ion transport through the porous hybrid network. Our study therefore illustrates the ability to adjust the dissolution properties of the core-shell system via surrounding temperature and, thus, control the release of Ca ions from the BG.

Self-Assembly of Core-Shell Hybrid Nanoparticles by Directional Crystallization of Grafted Polymers.

Nanoparticle self-assembly is an efficient bottom-up strategy for the creation of nanostructures. In a typical approach, ligands are grafted onto the surfaces of nanoparticles to improve the dispersion stability and control interparticle interactions. Ligands then remain secondary and usually are not expected to order significantly during superstructure formation. Here, we investigate how ligands can play a more decisive role in the formation of anisotropic inorganic-organic hybrid materials. We graft poly(2-iso-propyl-2-oxazoline) (PiPrOx) as a crystallizable shell onto SiO2 nanoparticles. By varying the PiPrOx grafting density, both solution stability and nanoparticle aggregation behavior can be controlled. Upon prolonged heating, anisotropic nanostructures form in conjunction with the crystallization of the ligands. Self-assembly of hybrid PiPrOx@SiO2 (shell@core) nanoparticles proceeds in two steps: First, the rapid formation of amorphous aggregates occurs via gelation, mediated by the interaction between nanoparticles through grafted polymer chains. As a second step, slow radial growth of fibers was observed via directional crystallization, governed by the incorporation of crystalline ribbons formed from free polymeric ligands in combination with crystallization of the covalently attached ligand shell. Our work reveals how crystallization-driven self-assembly of ligands can create intricate hybrid nanostructures.

Diiodo-BODIPY Sensitizing of the [Mo3S13]2- Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix.

We report on a photocatalytic setup that utilizes the organic photosensitizer (PS) diiodo-BODIPY and the non-precious-metal-based hydrogen evolution reaction (HER) catalyst (NH4)2[Mo3S13] together with a polyampholytic unimolecular matrix poly(dehydroalanine)-graft-poly(ethylene glycol) (PDha-g-PEG) in aqueous media. The system shows exceptionally high performance with turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h-1) that are typical for noble-metal-containing systems. Excited-state absorption spectra reveal the formation of a long-lived triplet state of the PS in both aqueous and organic media. The system is a blueprint for developing noble-metal-free HER in water. Component optimization, e.g., by modification of the meso substituent of the PS and the composition of the HER catalyst, is further possible.

Double hydrophilic copolymers - synthetic approaches, architectural variety, and current application fields.

Solubility and functionality of polymeric materials are essential properties determining their role in any application. In that regard, double hydrophilic copolymers (DHC) are typically constructed from two chemically dissimilar but water-soluble building blocks. During the past decades, these materials have been intensely developed and utilised as, e.g., matrices for the design of multifunctional hybrid materials, in drug carriers and gene delivery, as nanoreactors, or as sensors. This is predominantly due to almost unlimited possibilities to precisely tune DHC composition and topology, their solution behavior, e.g., stimuli-response, and potential interactions with small molecules, ions and (nanoparticle) surfaces. In this contribution we want to highlight that this class of polymers has experienced tremendous progress regarding synthesis, architectural variety, and the possibility to combine response to different stimuli within one material. Especially the implementation of DHCs as versatile building blocks in hybrid materials expanded the range of water-based applications during the last two decades, which now includes also photocatalysis, sensing, and 3D inkjet printing of hydrogels, definitely going beyond already well-established utilisation in biomedicine or as templates.

Controlling Growth of Poly (Triethylene Glycol Acrylate-Co-Spiropyran Acrylate) Copolymer Liquid Films on a Hydrophilic Surface by Light and Temperature.

A quartz crystal microbalance with dissipation monitoring (QCM-D) was employed for in situ investigations of the effect of temperature and light on the conformational changes of a poly (triethylene glycol acrylate-co-spiropyran acrylate) (P (TEGA-co-SPA)) copolymer containing 12-14% of spiropyran at the silica-water interface. By monitoring shifts in resonance frequency and in acoustic dissipation as a function of temperature and illumination conditions, we investigated the evolution of viscoelastic properties of the P (TEGA-co-SPA)-rich wetting layer growing on the sensor, from which we deduced the characteristic coil-to-globule transition temperature, corresponding to the lower critical solution temperature (LCST) of the PTEGA part. We show that the coil-to-globule transition of the adsorbed copolymer being exposed to visible or UV light shifts to lower LCST as compared to the bulk solution: the transition temperature determined acoustically on the surface is 4 to 8 K lower than the cloud point temperature reported by UV/VIS spectroscopy in aqueous solution. We attribute our findings to non-equilibrium effects caused by confinement of the copolymer chains on the surface. Thermal stimuli and light can be used to manipulate the film formation process and the film's conformational state, which affects its subsequent response behavior.

Polyampholytic Graft Copolymers as Matrix for TiO2 /Eosin Y/[Mo3 S13 ]2- Hybrid Materials and Light-Driven Catalysis.

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core-shell hybrid materials based on a TiO2 core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO2 ). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO2 core. This resulted in high visible-light-driven H2 generation. The enhanced light-driven catalytic activity is attributed to the unique core-shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO2 was possible by introducing [Mo3 S13 ]2- cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.

Triple-Responsive Polyampholytic Graft Copolymers as Smart Sensors with Varying Output.

Three triggers result in two measurable outputs from polymeric sensors: multiresponsive polyampholytic graft copolymers respond to pH-value and temperature, as well as the type and concentration of metal cations and therefore, allow the transformation of external triggers into simply measurable outputs (cloud point temperature (TCP ) and surface plasmon resonance (SPR) of encapsulated silver nanoparticles). The synthesis relies on poly(dehydroalanine) (PDha) as the reactive backbone and gives straightforward access to materials with tunable composition and output. In particular, a rather high sensitivity toward the presence of Cu2+ , Co2+ , and Pb2+ metal cations is found.

1,7,9,10-Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis.

In this work, we present a new synthetic strategy for fourfold-substituted perylene monoimides via tetrabrominated perylene monoanhydrides. X-ray diffraction analysis unveiled the intramolecular stacking orientation between the substituents and semicircular packing behavior. We observed the remarkable influence of the substituent on the longevity and nature of the excited state upon visible light excitation. In the presence of poly(dehydroalanine)-graft-poly(ethylene glycol) graft copolymers as solubilizing template, the chromophores are capable of sensitizing [Mo3 S13 ]2- clusters in aqueous solution for stable visible light driven hydrogen evolution over three days.