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Bioinspired Polydopamine Coating as an Adhesion Enhancer Between Paraffin Microcapsules and an Epoxy Matrix

2020, Fredi, Giulia, Simon, Frank, Sychev, Dmitrii, Melnyk, Inga, Janke, Andreas, Scheffler, Christina, Zimmerer, Cordelia

Microencapsulated phase change materials (PCMs) are attracting increasing attention as functional fillers in polymer matrices, to produce smart thermoregulating composites for applications in thermal energy storage (TES) and thermal management. In a polymer composite, the filler–matrix interfacial adhesion plays a fundamental role in the thermomechanical properties. Hence, this work aims to modify the surface of commercial PCM microcapsules through the formation of a layer of polydopamine (PDA), a bioinspired polymer that is emerging as a powerful tool to functionalize chemically inert surfaces due to its versatility and great adhesive potential in many different materials. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) evidenced that after PDA coating, the surface roughness increased from 9 to 86 nm, which is beneficial, as it allows a further increase in the interfacial interaction by mechanical interlocking. Spectroscopic techniques allowed investigating the surface chemistry and identifying reactive functional groups of the PDA layer and highlighted that, unlike the uncoated microcapsules, the PDA layer is able to react with oxirane groups, thereby forming a covalent bond with the epoxy matrix. Hot-stage optical microscopy and differential scanning calorimetry (DSC) highlighted that the PDA modification does not hinder the melting/crystallization process of the paraffinic core. Finally, SEM micrographs of the cryofracture surface of epoxy composites containing neat or PDA-modified microcapsules clearly evidenced improved adhesion between the capsule shell and the epoxy matrix. These results showed that PDA is a suitable coating material with considerable potential for increasing the interfacial adhesion between an epoxy matrix and polymer microcapsules with low surface reactivity. This is remarkably important not only for this specific application but also for other classes of composite materials. Future studies will investigate how the deposition parameters affect the morphology, roughness, and thickness of the PDA layer and how the layer properties influence the capsule–matrix adhesion.

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Thermophilic films and fibers from photo cross-linkable UCST-type polymers

2015, Liu, Fangyao, Jiang, Shaohua, Ionov, Leonid, Agarwal, Seema

Photo cross-linkable thermoresponsive polymers of UCST-type based on acrylamide (AAm) and acrylonitrile (AN) useful for preparing thermophilic hydrogel films and fibers are presented. The polymers prepared via free radical and reversible addition fragmentation chain-transfer (RAFT) polymerization methods using N-(4-benzoylphenyl)acrylamide (BPAm) as photo cross-linkable comonomers provided highly stable UCST-type phase transition in water reproducible without hysteresis for many cycles. The cloud point could be manipulated by varying the acrylonitrile amount in the feed. Chemically cross-linked hydrogel films and nanofibers (average diameter 500 nm) were successfully prepared from the ter-copolymers by solution casting and electrospinning followed by UV irradiation. These hydrogels showed a continuous positive volume transition behavior in water with increasing temperature that was utilized for the design of microactuators.

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Local delivery to malignant brain tumors: potential biomaterial-based therapeutic/adjuvant strategies

2021, Alghamdi, Majed, Gumbleton, Mark, Newland, Ben

Glioblastoma (GBM) is the most aggressive malignant brain tumor and is associated with a very poor prognosis. The standard treatment for newly diagnosed patients involves total tumor surgical resection (if possible), plus irradiation and adjuvant chemotherapy. Despite treatment, the prognosis is still poor, and the tumor often recurs within two centimeters of the original tumor. A promising approach to improving the efficacy of GBM therapeutics is to utilize biomaterials to deliver them locally at the tumor site. Local delivery to GBM offers several advantages over systemic administration, such as bypassing the blood-brain barrier and increasing the bioavailability of the therapeutic at the tumor site without causing systemic toxicity. Local delivery may also combat tumor recurrence by maintaining sufficient drug concentrations at and surrounding the original tumor area. Herein, we critically appraised the literature on local delivery systems based within the following categories: polymer-based implantable devices, polymeric injectable systems, and hydrogel drug delivery systems. We also discussed the negative effect of hypoxia on treatment strategies and how one might utilize local implantation of oxygen-generating biomaterials as an adjuvant to enhance current therapeutic strategies. © 2021 The Royal Society of Chemistry.

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Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization

2015, Mai, Tobias, Boye, Susanne, Yuan, Jiayin, Völkel, Antje, Gräwert, Marlies, Günter, Christina, Lederer, Albena, Taubert, Andreas

The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.

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Correlation of carbon nanotube dispersability in aqueous surfactant solutions and polymers

2009, Krause, Beate, Petzold, Gudrun, Pegel, Sven, Pötschke, Petra

In order to assess the dispersability of carbon nanotube materials, tubes produced under different synthesis conditions were dispersed in aqueous surfactant solutions and the sedimentation behaviour under centrifugation forces was investigated using a LUMiFuge stability analyzer. The electrical percolation threshold of the nanotubes after melt mixing in polyamide 6.6 was determined and the state of dispersion was studied. As a general tendency, the nanotubes having better aqueous dispersion stability showed lower electrical percolation threshold and better nanotube dispersion in the composites. This indicates that the investigation of the stability of aqueous dispersions is also able to give information about the nanotubes inherent dispersability in polymer melts, both strongly influenced by the entanglement and agglomerate structure of the tubes within the as-produced nanotube materials. The shape of the nanotubes in the aqueous dispersions was assessed using a SYSMEX flow particle image analyzer and found to correspond to the shape observed from cryofractured surfaces of the polymer composites. © 2008 Elsevier Ltd. All rights reserved.