Super-soft, firm, and strong elastomers toward replication of tissue viscoelastic response.

Polymeric networks are commonly used for various biomedical applications, from reconstructive surgery to wearable electronics. Some materials may be soft, firm, strong, or damping however, implementing all four properties into a single material to replicate the mechanical properties of tissue has been inaccessible. Herein, we present the A-g-B brush-like graft copolymer platform as a framework for fabrication of materials with independently tunable softness and firmness, capable of reaching a strength of ∼10 MPa on par with stress-supporting tissues such as blood vessel, muscle, and skin. These properties are maintained by architectural control, therefore diverse mechanical phenotypes are attainable for a variety of different chemistries. Utilizing this attribute, we demonstrate the capability of the A-g-B platform to enhance specific characteristics such as tackiness, damping, and moldability.

Bottlebrush Elastomers with Crystallizable Side Chains: Monitoring Configuration of Polymer Backbones in the Amorphous Regions during Crystallization.

Brush-like elastomers with crystallizable side chains hold promise for biomedical applications requiring the presence of two distinct mechanical states below and above body temperature: hard and supersoft. The hard semicrystalline state facilitates piercing of the body whereupon the material softens to match the mechanics of surrounding soft tissue. To understand the transition between the two states, the crystallization process was studied with synchrotron X-ray scattering for a series of brush elastomers with poly(ε-caprolactone) side chains bearing from 7 to 13 repeat units. The so-called bottlebrush correlation peak was used to monitor configuration of bottlebrush backbones in the amorphous regions during the crystallization process. In the course of crystallization, the backbones are expelled into the interlamellar amorphous gaps, which is accompanied by their conformational changes and leads to partitioning to unconfined (melt) and confined (semicrystalline) (conformational) states. The crystallization process starts by consumption of the unconfined macromolecules by the growing crystals followed by reconfiguration of macromolecules within the already grown spherulites.

Injectable bottlebrush hydrogels with tissue-mimetic mechanical properties.

Injectable hydrogels are desired in many biomedical applications due to their minimally invasive deployment to the body and their ability to introduce drugs. However, current injectables suffer from mechanical mismatch with tissue, fragility, water expulsion, and high viscosity. To address these issues, we design brush-like macromolecules that concurrently provide softness, firmness, strength, fluidity, and swellability. The synthesized linear-bottlebrush-linear (LBL) copolymers facilitate improved injectability as the compact conformation of bottlebrush blocks results in low solution viscosity, while the thermoresponsive linear blocks permit prompt gelation at 37°C. The resulting hydrogels mimic the deformation response of supersoft tissues such as adipose and brain while withstanding deformations of 700% and precluding water expulsion upon gelation. Given their low cytotoxicity and mild inflammation in vivo, the developed materials will have vital implications for reconstructive surgery, tissue engineering, and drug delivery applications.

Molecular patterns of oligopeptide hydrocarbons on graphite.

Graphitic materials including graphene, carbon nanotubes and fullerenes, are promising for use in nanotechnology and biomedicine. Non-covalent functionalization by peptides and other organic molecules allows changing the properties of graphitic surfaces in a controlled manner and represents a big potential for fundamental research and applications. Recently described oligopeptide-hydrocarbon derivative N,N'-(decane-1,10-diyl)bis(tetraglycineamide) (GM) is highly prospective for the development of graphitic interfaces in biosensor application as well as in structural biology for improving the quality of high-resolution atomic force microscopy (AFM) visualization of individual biomacromolecules. However, molecular organization of GM on graphitic surfaces is still unknown. In this work, the molecular model of GM at the water/highly oriented pyrolytic graphite (HOPG) interface has been developed basing on the high-resolution AFM and full-atom molecular modeling data. This model explains two periodicities observed in AFM images by GM self-assembly on a HOPG surface with formation of the stacks with the lateral shifts. The obtained results reveal the particular patterns and dynamics of GM molecules adsorbed on graphite and unravel the puzzle of peptide self-assembly on graphitic surfaces.

Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory-Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations.

Tissue-Adaptive Materials with Independently Regulated Modulus and Transition Temperature.

The ability of living species to transition between rigid and flexible shapes represents one of their survival mechanisms, which has been adopted by various human technologies. Such transition is especially desired in medical devices as rigidity facilitates the implantation process, while flexibility and softness favor biocompatibility with surrounding tissue. Traditional thermoplastics cannot match soft tissue mechanics, while gels leach into the body and alter their properties over time. Here, a single-component system with an unprecedented drop of Young's modulus by up to six orders of magnitude from the GPa to kPa level at a controlled temperature within 28-43 °C is demonstrated. This approach is based on brush-like polymer networks with crystallizable side chains, e.g., poly(valerolactone), affording independent control of melting temperature and Young's modulus by concurrently altering side chain length and crosslink density. Softening down to the tissue level at the physiological temperature allows the design of tissue-adaptive implants that can be inserted as rigid devices followed by matching the surrounding tissue mechanics at body temperature. This transition also enables thermally triggered release of embedded drugs for anti-inflammatory treatment.