Bottlebrush Networks: A Primer for Advanced Architectures.

Bottlebrush networks (BBNs) are an exciting new class of materials with interesting physical properties derived from their unique architecture. While great strides have been made in our fundamental understanding of bottlebrush polymers and networks, an interdisciplinary approach is necessary for the field to accelerate advancements. This review aims to act as a primer to BBN chemistry and physics for both new and current members of the community. In addition to providing an overview of contemporary BBN synthetic methods, we developed a workflow and desktop application (LengthScale), enabling bottlebrush physics to be more approachable. We conclude by addressing several topical issues and asking a series of pointed questions to stimulate conversation within the community.

Network Constitutional Isomers.

Bottlebrush networks designed to be constitutional isomers of each other were synthesized for the first time. These network constitutional isomers (NCIs) have significantly different mechanical properties depending on their kinetic chain lengths (RK), which are controlled by the monomer-to-initiator ratio. Specifically, the low frequency moduli, yield behavior, elongation at break, and adhesive strength of these NCIs are different at the same cross-link densities. The NCI concept is extended to include RKs' dispersity through the choice of the catalyst. These NCIs highlight the impact of living polymerization chemistry on network formation. The use of living polymerization chemistry to synthesize new networks, including NCIs, is expected to significantly advance the development of next-generation materials.

Dynamic changes to signal allocation rules in response to variable social environments in house mice.

Urine marking is central to mouse social behavior. Males use depletable and costly urine marks in intrasexual competition and mate attraction. We investigate how males alter signaling decisions across variable social landscapes using thermal imaging to capture spatiotemporal marking data. Thermal recording reveals fine-scale adjustments in urinary motor patterns in response to competition and social odors. Males demonstrate striking winner-loser effects in scent mark allocation effort and timing. Competitive experience primes temporal features of marking and modulates responses to scent familiarity. Males adjust signaling effort, mark latency, and marking rhythm, depending on the scent identities in the environment. Notably, recent contest outcome affects how males respond to familiar and unfamiliar urine. Winners increase marking effort toward unfamiliar relative to familiar male scents, whereas losers reduce marking effort to unfamiliar but increase to familiar rival scents. All males adjust their scent mark timing after a contest regardless of fight outcome, and deposit marks in more rapid bursts during marking bouts. In contrast to this dynamism, initial signal investment predicts aspects of scent marking days later, revealing the possibility of alternative marking strategies among competitive males. These data show that mice flexibly update their signaling decisions in response to changing social landscapes.

Bottlebrush Amphiphilic Polymer Co-Networks.

We report the synthesis of novel poly(ethylene glycol) and poly(dimethyl siloxane) (PEG and PDMS, respectively) bottlebrush amphiphilic polymer co-networks (B-APCNs) with high gel fractions by a grafting-through ring-opening metathesis polymerization. By varying the volume fraction of PEG (ϕPEG), we alter the crystallinity of the networks, achieving complete suppression of PEG crystallinity at ϕPEG=0.35. Furthermore, we show that the crystallinity of these networks can be tuned to alter their moduli. Through dynamic mechanical analysis, we show that the storage and loss moduli of networks with completely suppressed crystallinity (ϕPEG=0.35) behave similarly to a PDMS homopolymer bottlebrush network. These bottlebrush networks represent an unexplored architecture for the field of amphiphilic polymer co-networks.

Synthesis and characterization of poly(ethylene glycol) bottlebrush networks via ring-opening metathesis polymerization.

Herein it is reported how the overlap concentration (C*) can be used to overcome crosslinking due to diol impurities in commercial PEG, allowing for the synthesize of bottlebrush polymers with good control over molecular weight. Additionally, PEG-based bottlebrush networks are synthesized via ROMP, attaining high conversions with minimal sol fractions (<2%). The crystallinity and mechanical properties of these networks are then further altered by solvent swelling with phosphate buffer solution (PBS) and 1-ethyl-3-methylimidazolium ethyl sulfate/DCM cosolvents. The syntheses reported here highlight the potential of the bottlebrush network architecture for use in the rational design of new materials.

The Impact of Polymerization Chemistry on the Mechanical Properties of Poly(dimethylsiloxane) Bottlebrush Elastomers.

We compare the low-strain mechanical properties of bottlebrush elastomers (BBEs) synthesized using ring-opening metathesis and free radical polymerization. Through comparison of experimentally measured elastic moduli and those predicted by an ideal, affine model, we evaluate the efficiency of our networks in forming stress-supporting strands. This comparison allowed us to develop a structural efficiency ratio that facilitates the prediction of mechanical properties relative to polymerization chemistry (e.g., softer BBEs when polymerizing under dilute conditions). This work highlights the impact that polymerization chemistry has on the structural efficiency ratio and the resultant mechanical properties of BBEs with identical side chains, providing another "knob" by which to control polymer network properties.

Development and characterization of erythrosine nanoparticles with potential for treating sinusitis using photodynamic therapy.

BACKGROUND: Antimicrobial therapy for sinusitis has been shown to reduce or eliminate pathologic bacteria associated with rhinosinusitis and improve the symptoms associated with the disease. However, the continuing rise in antibiotic resistance, the ongoing problem with patient compliance, and the intrinsic difficulty in eradication of biofilms complicates antibiotic therapy. The introduction of photodynamic antimicrobial therapy (PAT) using erythrosine, a photosensitizer, could eliminate the bacteria without inducing antibiotic resistance or even requiring daily dosing. In the present study, erythrosine nanoparticles were prepared using poly-lactic-co-glycolic acid (PLGA) and evaluated for their potential in PAT against Staphylococcus aureus cells. METHODS: PLGA nanoparticles of erythrosine were prepared by nanoprecipitation technique. Erythrosine nanoparticles were characterized for size, zeta potential, morphology and in vitro release. Qualitative and quantitative uptake studies of erythrosine nanoparticles were carried out in S. aureus cells. Photodynamic inactivation of S. aureus cells in the presence of erythrosine nanoparticles was investigated by colony forming unit assay. RESULTS: Nanoprecipitation technique resulted in nanoparticles with a mean diameter of 385nm and zeta potential of -9.36mV. Erythrosine was slowly released from nanoparticles over a period of 120h. The qualitative study using flow cytometry showed the ability of S. aureus cells to internalize erythrosine nanoparticles. Moreover, erythrosine nanoparticles exhibited a significantly higher uptake and antimicrobial efficacy compared to pure drug in S. aureus cells. CONCLUSION: In conclusion, erythrosine-loaded PLGA nanoparticles can be a potential long term drug delivery system for PAT and are useful for the eradication of S. aureus cells.