Solvent-free synthesis of biostable segmented polyurethane shape memory polymers for biomedical applications.

Biostable shape memory polymers that remain stable in physiological conditions are beneficial for user-defined shape recovery in response to a specific stimulus. For potential commercialization and biocompatibility considerations, biomaterial synthesis must be simple and scalable. Hence, a library of biostable and cytocompatible shape memory polymers with tunable thermomechanical properties based on hard segment content was synthesized using a solvent-free method. Polymer surface chemistry, thermomechanical and shape memory properties, and biostability were assessed. We also investigated the effects of processing methods on thermomechanical and shape memory properties. All polymers showed high glass transition temperatures (>50 °C), which indicates that their temporary shape could be preserved after implantation. Polymers also demonstrate high shape fixity (73-80%) and shape recovery (93-95%). Minimal mass loss (<5%) was observed in accelerated oxidative (20% H2O2) and hydrolytic (0.1 M NaOH) media. Additionally, minimal shape recovery (∼0%) occurred in programmed samples with higher hard segment content that were stored in degradation media. After 40 days of storage in media, programmed samples recovered their primary shapes upon heating to temperatures above their transition temperature. Annealing to above the polymer melting point and solvent casting of polymers improved shape memory and thermal properties. To enable their potential use as biomaterial scaffolds, fiber formation of synthesized polyurethanes was compared with those of samples synthesized using a previously reported solvent-based method. The new method provided polymers that can form fibrous scaffolds with improved mechanical and shape memory properties, which is attributed to the higher molecular weight and crystalline content of polymers synthesized using the new, solvent-free approach. These biostable segmented polyurethanes could be coupled with a range of components that respond to specific stimuli, such as enzymes, magnetic field, pH, or light, to enable a specific shape change response, which could be coupled with drug and/or bioactive material delivery in future work.

Synthesis and Applications of Hybrid Polymer Networks Based on Renewable Natural Macromolecules.

Macromolecules obtained from renewable natural sources are gaining increasing attention as components for a vast variety of sustainable polymer-based materials. Natural raw materials can facilitate continuous-flow production due to their year-round availability and short replenishment period. They also open new opportunities for chemists and biologists to design and create "bioreplacement" and "bioadvantaged" polymers, where complex structures produced by nature are being modified, upgraded, and utilized to create novel materials. Bio-based macromonomers are expected not only to compete with but to replace some petroleum-based analogs, as well. The development of novel sustainable materials is an ongoing and very dynamic process. There are multiple strategies for transforming natural macromolecules into sophisticated value-added products. Some methods include chemical modification of macromolecules, while others include blending several components into one new system. One of the most promising approaches for incorporating renewable macromolecules into new products is the synthesis of hybrid networks based on one or more natural components. Each one has unique characteristics, so its incorporation into a network brings new sustainable materials with properties that can be tuned according to their end-use. This article reviews the current state-of-the-art and future potential of renewable natural macromolecules as sustainable building blocks for the synthesis and use of hybrid polymer networks. The most recent advancements and applications that involve polymers, such as cellulose, chitin, alginic acid, gellan gum, lignin, and their derivatives, are discussed.

Composite Hydrogels Based on Poly(Ethylene Glycol) and Cellulose Macromonomers as Fortified Materials for Environmental Cleanup and Clean Water Safeguarding.

Pollution with organic dyes is one of the most typical environmental problems related to industrial wastewater. The removal of these dyes opens up new prospects for environmental remediation, but the design of sustainable and inexpensive systems for water purification is a fundamental challenge. This paper reports the synthesis of novel fortified hydrogels that can bind and remove organic dyes from aqueous solutions. These hydrophilic conetworks consist of chemically modified poly(ethylene glycol) (PEG-m) and multifunctional cellulose macromonomers ("cellu-mers"). Williamson etherification with 4-vinylbenzyl chloride (4-VBC) is used to modify PEGs of different molecular masses (1, 5, 6, and 10 kDa) and cellobiose, Sigmacell, or Technocell™ T-90 cellulose (products derived from natural renewable resources) with polymerizable/crosslinkable moieties. The networks are formed with good (75%) to excellent (96%) yields. They show good swelling and have good mechanical properties according to rheological tests. Scanning electron microscopy (SEM) reveals that cellulose fibers are visibly embedded into the inner hydrogel structure. The ability to bind and remove organic dyes, such as bromophenol blue (BPB), methylene blue (MB), and crystal violet (CV), from aqueous solutions hints at the potential of the new cellulosic hydrogels for environmental cleanup and clean water safeguarding.

Stronger Together. Poly(Styrene) Gels Reinforced by Soft Gellan Gum.

This study targets the synthesis of novel semi-interpenetrating networks and amphiphilic conetworks, where hydrophilic soft matter (Gellan Gum, GG) was combined with hydrophobic rigid poly(styrene), PSt. To achieve that, GG was chemically modified with 4-vinyl benzyl chloride to form a reactive macromonomer with multiple double bonds. These double bonds were used in a copolymerization with styrene to initially form semi-interpenetrating networks (SIPNs) where linear PSt was intertwined within the GG-PSt conetwork. The interpenetrating linear PSt and unreacted styrene were extracted over 3 consecutive days with yields 18-24%. After the extraction, the resulting conetworks (yields 76-82%) were able to swell both in organic and aqueous media. Thermo-mechanical tests (thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis) and rheology indicated that both SIPNs and conteworks had, in most cases, improved thermal and mechanical properties compared to pure poly(styrene) and pure GG gels. This crosslinking strategy proved that the reactive combination of a synthetic polymer and a bio-derived constituent would result in the formation of more sustainable materials with improved thermo-mechanical properties. The binding ability of the amphiphilic conetworks towards several organic dyes was high, showing that they could be used as potential materials in environmental clean-up.

Reactive Cellu-mers-A Novel Approach to Improved Cellulose/Polymer Composites.

In this paper, we describe a novel method for preparation of polymer composites with homogeneous dispersion of natural fibers in the polymer matrix. In our approach, Williamson ether synthesis is used to chemically modify cellulose with polymerizable styrene moieties and transform it into a novel multifunctional cellu-mer that can be further crosslinked by copolymerization with styrene. Reactions with model compounds (cellobiose and cellotriose) successfully confirm the viability of the new strategy. The same approach is used to transform commercially available cellulose nanofibrils (CNFs) of various sizes: Sigmacell and Technocell™ 40, 90 and 150. The styrene-functionalized cellulose oligomers and CNFs are then mixed with styrene and copolymerized in bulk at 65 °C with 2,2'-azobisisobutyronitrile as initiator. The resulting composites are in a form of semi-interpenetrating networks (s-IPN), where poly(styrene) chains are either crosslinked with the uniformly dispersed cellulosic component or entangled through the network. Non-crosslinked poly(styrene) (31-41 w%) is extracted with CHCl3 and analyzed by size-exclusion chromatography to estimate the extent of homopolymerization and reveal the mechanism of the whole process. Electron microscopy analyses of the networks show the lack of cellu-mer agglomeration throughout the polymer matrix. The homogeneous distribution of cellulose entities leads to improved thermal and mechanical properties of the poly(styrene) composites compared to the physical mixtures of the same components and linear poly(styrene) of similar molecular mass.

Biofilm Removal by Reversible Shape Recovery of the Substrate.

Bacteria can colonize essentially any surface and form antibiotic resistant biofilms, which are multicellular structures embedded in an extracellular matrix secreted by the attached cells. To develop better biofilm control technologies, we recently demonstrated that mature biofilms can be effectively removed through on-demand shape recovery of a shape memory polymer (SMP) composed of tert-butyl acrylate (tBA). It was further demonstrated that such a dynamic substratum can sensitize the detached biofilm cells to antibiotics. However, this SMP can undergo shape change only once, limiting its application in long-term biofilm control. This motivated the present study, which aimed to prove the concept that biofilm can be effectively removed by repeated on-demand shape recovery. Reversible shape memory polymers (rSMPs) containing poly(ε-caprolactone) diisocyanatoethyl dimethacrylate (PCLDIMA) of varying molecular masses and butyl acrylate (BA) as a linker were synthesized by using benzoyl peroxide (BPO) as a thermal initiator. By comparison of several combinations of PCLDIMA of different molecular masses, a 2:1 weight ratio mixture of 2000 and 15000 g/mol PCLDIMA was the most promising because it had a shape transition (at 36.7 °C) close to body temperature. The synthesized rSMP demonstrated good reversible shape recovery and up to 94.3 ± 1.0% removal of 48 h Pseudomonas aeruginosa PAO1 biofilm cells after three consecutive shape recovery cycles. Additionally, the detached biofilm cells were found to be 5.0 ± 1.2 times more susceptible to 50 µg/mL tobramycin than the static control.