Epoxy-amine resins find wide application as the matrix material of high performance polymer composites because of their favorable mechanical properties, thermal properties and solvent stability. These properties result from the complicated, highly cross-linked molecular network that is characteristic of epoxy-amine thermoset polymers. The connectivity of the molecular network has a strong influence on the physical performance of the finished part. Nonhomogeneity in the network structure can degrade these favorable properties through the introduction of low-energy pathways for solvent penetration or fracture propagation. This work examines the influence of cure temperature on the network-building cross-linking reaction and the subsequent effect on the homogeneity of the cross-linked molecular network. Specific attention is paid to nanoscale variation in the distribution of cross-link density. Thermal, rheological, and spectroscopic techniques are used to monitor key chemical and structural changes during network growth. Atomic force microscopy is used to understand nanoscale fracture behavior in terms of the low energy pathways that result from a nonhomogeneous distribution of cross-link density. The influence of processing-induced changes in molecular connectivity is discussed in terms of observed nanoscale morphology and fracture properties of the cured material.

There remains a lack of fundamental understanding in the role of backbone rigidity on the thermomechanical properties of conjugated polymers. Here, we provide the first holistic approach to understand the fundamental influence of backbone rigidity on an n-type naphthalene diimide-based conjugated polymer, denoted by PNDI-Cx, through insertion of a flexible conjugation break spacer (CBS). CBS lengths are varied from fully conjugated with zero alkyl spacer (PNDI-C0) to a seven-carbon alkyl spacer (PNDI-C7), with the CBS engineered into each repeat unit for systematic evaluation. Solution small-angle neutron scattering and oscillatory shear rheometry were employed to provide the first quantitative evidence of CBS influence over conjugated polymer chain rigidity and entanglement molecular weight (M e), demonstrating a reduction in the Kuhn length from 521 to 36 Å for fully conjugated PNDI-C0 and PNDI-C6, respectively, as well as a nearly consistent M e of ∼15 kDa upon the addition of CBS. Thermomechanical properties, such as elastic modulus and glass-transition temperature, were shown to decrease with an increasing length of CBS. An extraordinary ductility, upwards of 400% tensile strain before fracture, was observed for high-molecular-weight PNDI-C4, which we attribute to a high number of entanglements and disruption of crystallization. Furthermore, the deformation mechanism for PNDI-Cx was studied under strain through X-ray diffraction, polarized UV–vis spectroscopy, and atomic force microscopy. Overall, this work sheds light on the important role of backbone rigidity in designing flexible and stretchable conjugated polymers.

Background: Oligomers of amyloid-␤ peptides are implicated in the etiology of Alzheimer disease. Results: Specific "off-pathway" oligomers of A␤42 show unique replication properties upon interacting with monomers. Conclusion:The results indicate that oligomers that are formed along pathways outside the fibril formation pathway may undergo replication. Significance: Mechanistic details of A␤ soluble oligomers will enable better understanding of Alzheimer disease pathology.

Antimicrobial peptides (AMPs) show great potential as alternative therapeutic agents to conventional antibiotics as they can selectively bind and eliminate pathogenic bacteria without harming eukaryotic cells. It is of interest to develop synthetic macromolecules that mimic AMPs behavior, but that can be produced more economically at commercial scale. Herein, we describe the use of aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare primary and tertiary amine-containing polymers with precise molecular weight control and narrow molecular weight distributions. Specifically, N-(3-aminopropyl)methacrylamide (APMA) was statistically copolymerized with N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) or N-[3-(diethylamino)propyl]methacrylamide (DEAPMA) to afford a range of (co)polymer compositions. Analysis of antimicrobial activity against E. coli (Gram-negative) and B. subtilis (Gram-positive) as a function of buffer type, salt concentration, pH, and time indicated that polymers containing large fractions of primary amine were most effective against both strains of bacteria. Under physiological pH and salt conditions, the polymer with the highest primary amine content caused complete inhibition of bacterial growth at low concentrations, while negligible hemolysis was observed over the full range of concentrations tested, indicating exceptional selectivity. The cytotoxicity of select polymers was evaluated against MCF-7 cells.