Effect of Polymer Porosity on Aqueous Self‐ H ealing Encapsulation of Proteins in PLGA Microspheres

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102254/1/mabi201300323.pd

Design of semi-interpenetrating networks based on poly(ethyl-2-cyanoacrylate) and oligo(ethylene glycol) diglycidyl ether

The synthesis of semi-interpenetrating networks (SIPN) based on linear poly(ethyl 2- cyanoacrylate) (PECA) and oligo(ethylene glycol) diglycidyl ether (OEGDG) based polymer networks was motivated by the hypothesis that the brittleness of polycyanoacrylates may be overcome by incorporating them into a polymer network architecture. A sequential synthetic route was applied, in which first PECA was prepared by anionic polymerization. Subsequently, OEGDG was crosslinked with different anhydrides and curing catalysts to form networks with hydrolyzable ester bonds and interpenetrating PECA. These SIPNs showed a low water uptake compared to other polyether based networks. Some of the obtained materials were transparent and exhibited a great flexibility, which was maintained also after 24 h of immersion in water and subsequent drying. Such networks could be components of future stimuli-sensitive material systems

Chitosan scaffolds with a shape memory effect induced by hydration

We demonstrate that chitosan-based porous scaffolds can present a shape memory effect triggered by hydration. The shape memory effect of non-crosslinked (CHT0) and genipin-crosslinked (CHT1) scaffolds was followed by innovative hydromechanical compressive tests and dynamic mechanical analysis (DMA), while the sample was immersed in varying compositions of water–ethanol mixtures. By dehydration with higher contents of ethanol, the vitreous-like nature of the amorphous component of chitosan allows the fixation of the temporary shape of the scaffold. The presence of water disrupts inter-molecular hydrogen bonds permitting large-scale segmental mobility of the chitosan chains upon the occurrence of glass transition and thus the recovery of the permanent shape of a pre-deformed scaffold. Results showed that chitosan possesses shape memory properties, characterized by a fixity ratio above 97.2% for CHT0 and above 99.2% for CHT1 and a recovery ratio above 70.5% for CHT0 and 98.5% for CHT1. In vitro drug delivery studies were also performed to demonstrate that such devices can also be loaded with molecules. We show that the developed chitosan scaffolds are candidates of biomaterials for applications in minimally invasive surgery for tissue regeneration or for drug delivery.This work was supported by the Portuguese Foundation for Science and Technology Foundation (FCT) through project PTDC/FIS/115048/2009. We acknowledge Dr Ana Rita Duarte for all the help during this project and Joana Marques Silva and So. a Caridade for their contribution to the DMA experiments

Hydrolytic Degradation Behavior of Poly(rac-lactide)-block-poly(propylene glycol)-block-poly(rac-lactide) Dimethacrylate Derived Networks Designed for Biomedical Applications

For polymer-based degradable implants, mechanical performance and degradation behavior need to be precisely controlled. Based on a rational design, this work comprehensively describes the properties of photo-crosslinked polymer networks prepared from poly(rac-lactide)-block-poly(propylene glycol)-block-poly(rac-lactide) dimethacrylate precursors during degradation. By varying the length of poly(rac-lactide) blocks connected to a central 4?kDa polyether block, microphase separated networks with adjustable crosslinking density, hydrophilicity/hydrophobicity ratio, thermal, and mechanical properties are obtained. The materials are characterized by a low water uptake, controlled mass loss, and slowly decreasing wet-state E moduli in the kPa range

Shape-memory properties of magnetically active triple-shape nanocomposites based on a grafted polymer network with two crystallizable switching segments

Thermo-sensitive shape-memory polymers (SMP), which are capable of memorizing two or more different shapes, have generated significant research and technological interest. A triple-shape effect (TSE) of SMP can be activated e.g. by increasing the environmental temperature (Tenv), whereby two switching temperatures (Tsw) have to be exceeded to enable the subsequent shape changes from shape (A) to shape (B) and finally the original shape (C). In this work, we explored the thermally and magnetically initiated shape-memory properties of triple-shape nanocomposites with various compositions and particle contents using different shape-memory creation procedures (SMCP). The nanocomposites were prepared by the incorporation of magnetite nanoparticles into a multiphase polymer network matrix with grafted polymer network architecture containing crystallizable poly(ethylene glycol) (PEG) side chains and poly(ε-caprolactone) (PCL) crosslinks named CLEGC. Excellent triple-shape properties were achieved for nanocomposites with high PEG weight fraction when two-step programming procedures were applied. In contrast, single-step programming resulted in dual-shape properties for all investigated materials as here the temporary shape (A) was predominantly fixed by PCL crystallites

First Jump of Microgel: Actuation Speed Enhancement by Elastic Instability

Swelling-induced snap-buckling in a 3D micro hydrogel device, inspired by the insect-trapping action of Venus flytrap, makes it possible to generate astonishingly fast actuation. We demonstrate that elastic energy is effectively stored and quickly released from the device by incorporating elastic instability. Utilizing its rapid actuation speed, the device can even jump by itself upon wetting.Comment: 4 pages, 3 figure

Periodic thermomechanical modulation of toll-like receptor expression and distribution in mesenchymal stromal cells

Toll-like receptor (TLR) can trigger an immune response against virus including SARS-CoV-2. TLR expression/distribution is varying in mesenchymal stromal cells (MSCs) depending on their culture environments. Here, to explore the effect of periodic thermomechanical cues on TLRs, thermally controlled shape-memory polymer sheets with programmable actuation capacity were created. The proportion of MSCs expressing SARS-CoV-2-associated TLRs was increased upon stimulation. The TLR4/7 colocalization was promoted and retained in the endoplasmic reticula. The TLR redistribution was driven by myosin-mediated F-actin assembly. These results highlight the potential of boosting the immunity for combating COVID-19 via thermomechanical preconditioning of MSCs

The response of human induced pluripotent stem cells to cyclic temperature changes explored by BIO-AFM

Human induced pluripotent stem cells (hiPSCs) are highly sensitive to extrinsic physical and biochemical signals from their extracellular microenvironments. In this study, we analyzed the effect of cyclic temperature changes on hiPSCs behaviors, especially by means of scanning force microscopy (BIO-AFM). The alternation in cellular mechanics, as well as the secretion and pattern of deposition of extracellular matrix (ECM) protein in hiPSCs were evaluated. The arrangement of the actin cytoskeleton changed with the variation of the temperature. The rearranged cytoskeleton architecture led to the subsequent changes in cell mechanics (Young's modulus of hiPSCs). With the exposure to the cyclic cold stimuli, an increase in the average surface roughness (Ra) and roughness mean square (RMS) was detected. This observation might be at least in part due to the upregulated secretion of Laminin α5 during repeated temporary cooling. The expression of pluripotent markers, NANOG and SOX2, was not impaired in hiPSCs, when exposed to the cyclic cold stimuli for 24 h. Our findings provide an insight into the effect of temperature on the hiPSC behaviors, which may contribute to a better understanding of the application of locally controlled therapeutic hypothermia

Polydopamine-based biofunctional substrate coating promotes mesenchymal stem cell migration

Rapid migration of mesenchymal stem cells (MSCs) on device surfaces could support in vivo tissue integration and might facilitate in vitro organoid formation. Here, polydopamine (PDA) is explored as a biofunctional coating to effectively promote MSC motility. It is hypothesized that PDA stimulates fibronectin deposition and in this way enhances integrin-mediated migration capability. The random and directional cell migration was investigated by time-lapse microscopy and gap closure assay respectively, and analysed with softwares as computational tools. A higher amount of deposited fibronectin was observed on PDA substrate, compared to the non-coated substrate. The integrin β1 activation and focal adhesion kinase (FAK) phosphorylation at Y397 were enhanced on PDA substrate, but the F-actin cytoskeleton was not altered, suggesting MSC migration on PDA was regulated by integrin initiated FAK signalling. This study strengthens the biofunctionality of PDA coating for regulating stem cells and offering a way of facilitating tissue integration of devices