In this study we use poly(-isopropylacrylamide) (PNIPAM) based copolymer microgels to create free-standing, transferable, thermoresponsive membranes. The microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)-benzophenone (HMABP) and spin-coated on Si wafers. After subsequent cross-linking by UV-irradiation, the formed layers easily detach from the supporting material. We obtain free standing microgel membranes with lateral extensions of several millimetres and an average layer thickness of a few hundred nanometres. They can be transferred to other substrates. As one example for potential applications we investigate the temperature dependent ion transport through the membranes resistance measurements revealing a sharp reversible increase in resistance when the lower critical solution temperature of the copolymer microgels is reached. In addition, prior to cross-linking, the microgels can be decorated with silver nanoparticles and cross-linked afterwards. Such free-standing nanoparticle hybrid membranes are then used as catalytic systems for the reduction of 4-nitrophenol, which is monitored by UV/Vis spectroscopy.
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http://dx.doi.org/10.1039/d1ra03528b | DOI Listing |
ACS Nano
January 2025
Department of Orthopedics, The First Affiliated Hospital of Soochow University, 899 Pinghai Road, Soochow, Jiangsu 215000, China.
The extracellular matrix (ECM) stores signaling molecules and facilitates mechanical and biochemical signaling in cells. However, the influence of biomimetic "rejuvenation" ECM structures on aging- and degeneration-related cellular activities and tissue repair is not well understood. We combined physical extrusion and precise "on-off" alternating cross-linking methods to create anisotropic biomaterial microgels (MicroRod and MicroSphere) and explored how they regulate the cell activities of the nucleus pulposus (NP) and their potential antidegenerative effects on intervertebral discs.
View Article and Find Full Text PDFAdv Mater
December 2024
Dynamic Colloidal Systems Laboratory, Department of Chemistry, Indian Institute of Technology, Roorkee, 247667, India.
The design of chemomechanical self-oscillators, which execute oscillations in the presence of constant stimuli lacking periodicity, is a step toward the development of autonomous and interactive soft robotic systems. This work presents a simple design of prolonged chemomechanical oscillatory movement in a microgel system capable of buoyant motility within stratified chemical media containing spatially localized sinking and floating stimuli. Three design elements are developed: a stimuli-responsive membranized calcium alginate microgel, a Percoll density gradient for providing stratified antagonistic chemical media, and transduction of microgel particle size actuation into buoyant motility via membrane-mediated displacement of the Percoll media.
View Article and Find Full Text PDFBiomater Adv
March 2025
Center for Biomaterials and Tissue Engineering (CBIT), Universitat Politècnica de València, Valencia, Spain; CIBER de Bioinginiería, Biomateriales y Nanomedicina, Instituto de Salud Carlos III, Spain.
Articular cartilage has limited regenerative capacity, so focal lesions generate mechanical stress in the joint that induces an aggravation of the damage, which ultimately leads to osteoarthritis. We recently suggested the use of microgels at the site of the cartilage defect, as a support material, to generate a biomechanical environment where pluripotent cells differentiate towards the hyaline cartilage phenotype. Here we propose a chondral regeneration strategy based on subchondral bone injury, and filling the defect site with an agglomerate of two types of microspheres, some rigid made of a biodegradable polyester (40 μm mean diameter), and others with a gel consistency made of platelet-rich plasma obtained from circulating blood (70-110 μm diameter).
View Article and Find Full Text PDFBioconjug Chem
December 2024
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Conjugates of the biocompatible polysaccharide pullulan with a cell membrane permeabilizing peptide L17E (PL-L17Es) were prepared with the aim of producing complex coacervates with pronounced intracellular antibody (IgG) delivery activity and stable structures. Coacervates with diameters of a few μm were formed simply by mixing PL-L17Es with IgG labeled with negatively charged fluorescent moieties of Alexa Fluor 488 [IgG(AF488)]. The coacervate resulted in a pronounced cytosolic infusion of IgG(AF488) and IgG binding to the target proteins inside the cell.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
Institut für Physikalische Chemie I: Kolloide und Nanooptik, Heinrich-Heine-Universität Düsseldorf, Universitätsstr. 1, 40225, Düsseldorf, Germany.
Thin films made of deformable micro- and nano-units, such as biological membranes, polymer interfaces, and particle-laden liquid surfaces, exhibit a complex behavior during drying, with consequences for various applications like wound healing, coating technologies, and additive manufacturing. Studying the drying dynamics and structural changes of soft colloidal films thus holds the potential to yield valuable insights to achieve improvements for applications. In this study, interfacial monolayers of core-shell (CS) microgels with varying degrees of softness are employed as model systems and to investigate their drying behavior on differently modified solid substrates (hydrophobic vs hydrophilic).
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