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Polymer networks remain an essential class of soft materials. Despite their use in everyday materials, connecting the molecular structure of the network to its macroscopic properties remains an active area of research. Much current research is enabled by advances in modern polymer chemistry providing an unprecedented level of control over macromolecular structure. At the same time, renewed interest in self‐healing, dynamic, and/or adaptable materials continues to drive substantial interest in polymer network design. As part of a special issue focused on research performed in the Polymer Science and Engineering Department at the University of Massachusetts, Amherst, this review highlights connections between macromolecular structure of networks and observed mechanical properties as investigated by the Tew research group. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Sum frequency generation (SFG) vibrational spectroscopy was used to study interactions between solid-supported lipid bilayers mimicking microbial and erythrocyte cellular membranes and synthetic antimicrobial arylamide oligomers named 2, 3, and 4, designed with the facial amphiphilicity common to naturally occurring antimicrobial peptides. The three compounds have the same backbone structure but varied side chains. The inherent interracial sensitivity of SFG allowed for simultaneous monitoring of lipid ordering in the individual bilayer leaflets and orientation of 2, 3, and 4 upon interaction with the bilayer. Critical concentrations at which the inner leaflet is disrupted were determined for each oligomer. Spectral evidence of the oligomers' interaction with the bilayer below the critical concentrations was also found. Oligomers 2 and 3 tilted toward the bilayer surface normal, in agreement with previous experimental and simulation results. These oligomers selectively interact with microbial membrane models over erythrocyte membrane models, correlating well to previously published SFG studies on antimicrobial oligomer 1. It was shown that the oligomers interact with the lipid bilayers differently, indicating their different activity and selectivity. This research further shows that SFG is a particularly useful technique for the investigation of interaction mechanisms between cell membranes and membrane-active molecules. Additionally, SFG provides details of the specific interactions between these novel antimicrobials and lipid bilayers. 10.1021/ac901271f

The human-mediated use and abuse of classical antibiotics has created a strong selective pressure for the rapid evolution of antibiotic resistance. As resistance levels rise, and the efficacy of classical antibiotics wanes, the intensity of the search for alternative antimicrobials has increased. One class of molecules that has attracted much attention is the antimicrobial peptides (AMPs). They exhibit broad-spectrum activity, they are potent and they are widespread as part of the innate defence system of both vertebrates and invertebrates. However, peptides are complex molecules that suffer from proteolytic degradation. The ability to capture the essential properties of antimicrobial peptides in simple easy-to-prepare molecules that are abiotic in origin and non-proteolytic offers many advantages. Mechanistic and structural knowledge of existing AMPs was used to design a novel compound that mimics the biochemical activity of an AMP. This report describes the development and in vitro characterization of a small peptide mimic that exhibited quick-acting and selective antibacterial activity against a broad range of bacteria, including numerous clinically relevant strains, at low MIC values.

Sum frequency generation (SFG) vibrational spectroscopy is employed to study the molecular interactions between a single substrate supported lipid bilayer and an amphiphilic antibiotic compound with a designed based on the common structural motif of natural antimicrobial peptides. The interfacial sensitivity of SFG allows real-time in situ monitoring of ordering changes in both leaflets of the bilayer and orientation of the compound simultaneously.

Oligomers based on an o-phenylene ethynylene (oPE) backbone with polar substituents are synthesized and folding of these extremely short oligomers is confirmed by 1D and 2D (NOESY) NMR methods. Variations of the oPEs are synthesized to determine the folded stability of pi-rich vs pi-poor vs pi-rich-pi-poor systems and to report an NMR solution characterization of folding for a PE backbone without hydrogen bonds.

Amphiphilic polymers based on modular norbornene derivatives exhibit good antibacterial activities and high selectivity for bacteria versus red blood cells. The study showed the preparation of fully synthetic high molecular weight polymers that mimic the activities of host-defensive peptides in the absence of a specific secondary structure.