Glycopolymers are an important class of biomaterials which include carbohydrate moieties in their polymer structure.
Nature achieves remarkable function from the formation of transient, nonequilibrium materials realized through continuous energy input. The role of enzymes in catalyzing chemical transformations to drive such processes, often as part of stimulidirected signaling, governs both material formation and lifetime. Inspired by the intricate nonequilibrium nanostructures of the living world, this work seeks to create transient materials in the presence of a consumable glucose stimulus under enzymatic control of glucose oxidase. Compared to traditional glucose-responsive materials, which typically engineer degradation to release insulin under highglucose conditions, the transient nanofibrillar hydrogel materials here are stabilized in the presence of glucose but destabilized under conditions of limited glucose to release encapsulated glucagon. In the context of blood glucose control, glucagon offers a key antagonist to insulin in responding to hypoglycemia by signaling the release of glucose stored in tissues so as to restore normal blood glucose levels. Accordingly, these materials are evaluated in a prophylactic capacity in diabetic mice to release glucagon in response to a sudden drop in blood glucose brought on by an insulin overdose. Delivery of glucagon using glucose-fueled nanofibrillar hydrogels succeeds in limiting the onset and severity of hypoglycemia in mice. This general strategy points to a new paradigm in glucose-responsive materials, leveraging glucose as a stabilizing cue for responsive glucagon delivery in combating hypoglycemia. Moreover, compared to most fundamental reports achieving nonequilibrium and/or fueled classes of materials, the present work offers a rare functional example using a disease-relevant fuel to drive deployment of a therapeutic.
A bioinspired, modular terpolymer adhesive, poly(N-methacryloyl-3,4-dihydroxyl-l-phenylalanine-co-9-(acryloyloxy)butyl anthracene-9-carboxylate-co-acrylic acid), has been synthesized containing three different functionalities: a photo-cross-linking segment, a wet interfacial adhesion segment, and a water-soluble segment. The synthesized adhesive polymer is the first example of a single-phase, photo-cross-linkable adhesive which does not require additional photoinitiator or other cross-linking agents. The terpolymer demonstrates strong adhesion when it swells in water and/or ethanol. The terpolymer is composed of three repeating units: N-methacryloyl-3,4-dihydroxyl-l-phenylalanine (MDOPA), which has been known to generate strong adhesion under wet conditions, poly(acrylic acid), which has been known to increase water solubility of polymers, and a photo-cross-linking segment consisting of an anthracene-based monomer used for enhancement of cohesion properties via UV irradiation (352 nm). A photomediated [4 + 4] cycloaddition reaction of anthracene results in the cross-linking of individual polymer chains after interfacial adhesion between substrates and adhesive polymers. Chemically, the covalent photo-cross-linking was confirmed by UV-vis, H NMR, and gel permeation chromatography (GPC). The cross-linking-fortified cohesion of the adhesive polymer network yields strengthened cohesion properties of the bulk material. The photoreaction was conveniently controlled via the duration of UV-irradiation. The adhesion properties of new adhesives were characterized by lap shear strength on transparent Mylar film and glasses after the adhesive was swollen in biologically friendly solvents including water and ethanol. The adhesion strength (J/m) was enhanced by 850% under 352 nm UV-irradiation. Multiple application variables were tested to determine the optimal conditions, such as solvent, concentration, polymer composition, and substrate. The best adhesion properties were obtained from a 1:1 weight ratio of polymer:solvent in water on a Mylar film surface. As a single-phase system, the synthesized terpolymer is very convenient to use, and its adhesion strength can be easily modified by UV light. Additionally, the terpolymer's high water compatibility makes it ideally suited for application in the biomedical field.
A new terpolymer adhesive, poly(2-methoxyethyl acrylate-co-N-methacryloyl 3,4-dihydroxyl-l-phenylalanine-co-heptaisobutyl substituted polyhedral oligomeric silsesquioxane propyl methacrylate) (poly(MEA-co-MDOPA-co-MPOSS) was synthesized by thermally initiated radical polymerization. In this study, we investigated the effect of the POSS component on adhesion, mechanical, and optical properties of the catechol-group containing bioinspired adhesives. The terpolymer contains the catechol group which is known to improve the adhesion properties of polymers. Only a very small amount of the POSS-containing monomer, MPOSS, was included, 0.5 mol %. In the presence of POSS, the synthesized poly(MEA-co-MDOPA-co-MPOSS) demonstrated strong adhesion properties, 23.2 ± 6.2 J/m with 0.05 N preloading and 300 s holding time, compared to many previously prepared catechol-containing adhesives. The mechanical properties (Young's modulus and stress at 10% strain) of the POSS-containing terpolymer showed significant increases (6-fold higher) over the control polymer, which does not contain POSS. Optical transmittance of the synthesized terpolymer was also improved significantly in the visible light range, 450-750 nm. Cell testing with human embryonic kidney cells (HEK293A) indicates that the new terpolymer is a promising candidate in biomedical adhesives without acute cytotoxicity. The synthesized poly(MEA-co-MDOPA-co-MPOSS) is the first example of POSS-containing pressure sensitive bioinspired adhesive for biomedical applications. The study of poly(MEA-co-MDOPA-co-MPOSS) demonstrated a convenient method to enhance two important properties, mechanical and optical properties, by the addition of a very small amount of POSS. Based on this study, it was found that POSS can be used to strengthen mechanical properties of bioinspired adhesive without the need for a covalent cross-linking step.
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