Triple‐responsive polyampholytic graft copolymers as smart sensors with varying output

Abstract 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 (T CP ) 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 Cu 2+ , Co 2+ , and Pb 2+ metal cations is found

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

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 the standard approach, ligands are grafted on the surfaces of nanoparticles to keep them separated 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 primary role in the formation of inorganic-organic hybrid materials. We graft poly(2-iso-propyl-2-oxazoline) (PiPrOx) as a crystallizable shell onto SiO$_2$ nanoparticles. By varying the PiPrOx grafting density, 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@SiO$_2$ (shell@core) nanoparticles proceeds in two steps: First, rapid formation of amorphous aggregates via gelation, mediated by the interaction between nanoparticles through grafted polymers; second, slow radial growth of fibers via directional crystallization, governed by the incorporation of crystalline ribbons formed from unbound polymers coupling to the grafted polymer shell. Our work reveals how crystallization-driven self-assembly of ligands can create intricate hybrid nanostructures.Comment: 12 pages, 5 figure

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 [Mo3S13]2− clusters in aqueous solution for stable visible light driven hydrogen evolution over three days. © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH Gmb

Hybrid materials based on water-soluble polymers: preparation and application in sensing and photocatalysis

This thesis describes the strategies for the innovative design of polymeric organic-inorganic hybrid materials using the development of synthetic approaches. The key objective of reported designs here is the excellent engineering of organic and inorganic building units that can successfully organize into target architecture of hybrid materials with ordered structures. Hereby, this thesis explains the strategies and corresponding their methods and results within three main chapters which cover (i): the synthesis of (co)polymer and semiconductor/metal nanoparticles (NP) (ii): solution behavior and crystallization-driven self-assembly of hybrid materials, and (iii): the application of the obtained organic-inorganic hybrid materials in photocatalysis and the sensing of heavy metal ions. In the first part of this thesis, we describe the synthesis of mostly double-hydrophilic graft and block (co)polymers to be used as templates and to form the shell in hybrid materials such as noble metals or CdS NP and core-shell hybrid materials like polymer@SiO2 and TiO2 nanoparticles. The second part focuses on the self-assembly of (co)polymers and hybrid materials using the crystallization-driven self-assembly (CDSA) approach. The last part is focusing on exploring the performance of copolymer-containing hybrid materials in various applications. To cut a long story short, this thesis describes straight-forward methods to tailor organic-inorganic hybrid materials to create appropriate and unprecedented hierarchical superstructures or hybrid materials for a variety of applications including directional self-assembly, metal sensors, water splitting, and immobilization of organic and inorganic nanomaterials