Adenine as an organocatalyst for the ring-opening polymerization of lactide: scope, mechanism and access to adenine-functionalized polylactide

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly, and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. In this study, we assess adenine as an organoinitiator/ organocatalyst for the ring-opening polymerization of lactide. L-Lactide can be quantitatively polymerized in the presence of adenine. Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine end-capped polylactide in a simple one-step procedure, in bulk, without additional catalyst. DFT calculations show that the polymerization occurs via hydrogen bond catalysis. The mechanism involves (i) a hydrogen bond between the NH9 of adenine and the carbonyl moiety of lactide, leading to an electron deficient carbon atom, and (ii) a second hydrogen bond between the N3 of adenine and the NH2 of a second adenine molecule, followed by a nucleophilic attack of the latter activated amine on the former electron deficient carbon on the monomer. For longer reaction times and higher temperatures, macrocyclic species are formed, and a mechanism involving the imidazole ring of adenine is proposed based on literature studies. Depending on the reaction conditions, adenine can thus be considered as an organoinitiator or an organocatalyst for the ring-opening polymerization of lactide.

Adenine as an organocatalyst for the ring-opening polymerization of lactide: scope, mechanism and access to adenine-functionalized polylactide

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly, and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. In this study, we assess adenine as an organoinitiator/organocatalyst for the ring-opening polymerization of lactide. L-Lactide can be quantitatively polymerized in the presence of adenine. Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine end-capped polylactide in a simple one-step procedure, in bulk, without additional catalyst. DFT calculations show that the polymerization occurs via hydrogen bond catalysis. The mechanism involves (i) a hydrogen bond between the NH9 of adenine and the carbonyl moiety of lactide, leading to an electron deficient carbon atom, and (ii) a second hydrogen bond between the N3 of adenine and the NH2 of a second adenine molecule, followed by a nucleophilic attack of the latter activated amine on the former electron deficient carbon on the monomer. For longer reaction times and higher temperatures, macrocyclic species are formed, and a mechanism involving the imidazole ring of adenine is proposed based on literature studies. Depending on the reaction conditions, adenine can thus be considered as an organoinitiator or an organocatalyst for the ring-opening polymerization of lactide.

Effects of pitch area-restrictions on tactical behavior, physical and physiological performances in soccer large-sided games

The aim of this study was to identify how pitch area-restrictions affects the tactical behavior, physical and physiological performances of players during soccer large-sided games. A 10 vs. 9 large-sided game was performed under three experimental conditions: (i) restricted-spacing, the pitch was divided into specific areas where players were assigned and they should not leave it; (ii) contiguous-spacing, the pitch was divided into specific areas where the players were only allowed to move to a neighboring one; (iii) free-spacing, the players had no restrictions in space occupation. The positional data were used to compute players’ spatial exploration index and also the distance, coefficient of variation, approximate entropy and frequency of near-in-phase displacements synchronization of players’ dyads formed by the outfield teammates. Players’ physical and physiological performances were assessed by the distance covered at different speed categories, game pace and heart rate. Most likely higher values were found in players’ spatial exploration index under free-spacing conditions. The synchronization between dyads’ displacements showed higher values for contiguous-spacing and free-spacing conditions. In contrast, for the jogging and running intensity zones, restricted-spacing demanded a moderate effect and most likely decrease compared to other scenarios (~20-50% to jogging and ~60-90% to running). Overall, the effects of limiting players’ spatial exploration greatly impaired the co-adaptation between teammates’ positioning while decreasing the physical and physiological performances. These results allow for a better understanding of players’ decision-making process according to specific task rules and can be relevant to enrich practice task design, such that coaches acknowledge the differential effect by using specific pitch-position areas restrictions.