Crystallization-Induced Self-Assembly of Poly(ethylene glycol) Side Chains in Dithiol-yne-Based Comb Polymers: Side Chain Spacing and Molecular Weight Effects.

The chain architecture and topology of macromolecules impact their physical properties and final performance, including their crystallization process. In this work, comb polymers constituted by poly(ethylene glycol), PEG, side chains, and a dithiol-yne-based ring polymer backbone have been studied, focusing on the micro- and nanostructures of the system, thermal behavior, and crystallization kinetics. The designed comb system allows us to investigate the role of a ring backbone, the impact of varying the distance between two neighboring side chains, and the effect of the molecular weight of the side chain. The results reflect that the governing factor in the crystalline properties is the molar mass of the side chains and that the tethering of PEG chains to the ring backbone brings important constraints to the crystallization process, reducing the crystallinity degree and slowing down the crystallization kinetics in comparison to analogue PEG homopolymers. We demonstrate that the effect of spatial hindrance in the comb-like PEG polymers drives the morphology toward highly ordered, self-assembled, semicrystalline superstructures with either extended interdigitated chain crystals or novel (for comb polymers) interdigitated folded chain lamellar crystals. These structures depend on PEG molecular weight, the distance between neighboring tethered PEG chains, and the crystallization conditions (nonisothermal versus isothermal). This work sheds light on the role of chain architecture and topology in the structure of comb-like semicrystalline polymers.

Ozone-induced changes in the content of bioactive compounds and enzyme activity during storage of pepper fruits.

This paper presents for the first time the results of investigations concerning the effect of treatment of whole pepper fruits with gaseous ozone and the refrigeration storage period conditions on pepper quality. The effects are reflected in changes in the flavonoid contents, the antioxidant activity of the phenolic compound fraction and the enzymes involved in phenylpropanoid metabolism. The investigations were carried out on a hot pepper fruit cultivar, Cyklon. It was found that the levels of a majority of flavonoids, in particular those of quercetin 3-O-rhamnoside and quercetin 3-O-rhamnoside-7-O-glucoside increased in the pericarp of fruits treated with ozone for 3h and stored for 20days (by 25% relative to the control). Simultaneously, reduced phenylalanine ammonia-lyase and tyrosine ammonia-lyase activity were noted, which implies slight degradation of enzymes caused by the ozone treatment and enhancement of the polyphenol oxidase and guaiacol oxidase activity involved in response to increased oxidative stress.