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.

DFT STUDIES ON THE MECHANISM OF RING-OPENING POLYMERIZATION OF LACTIDE WITH ADENINE

The use of organic molecules as catalysts for the ring-opening polymerization (ROP) of cyclic esters has gained much interest last years.[1] The use of a molecule of biological interest, able to initiate ROP of cyclic esters without any cocatalyst is even more interesting, as the resulting material will not contain any catalytic residue. Nucleobase-polymer conjugates development is thus an emerging area envisaging biomedical applications.[2] However, they are usually synthesized by tedious multistep procedures. Recently, adenine was used as organoinitiator for the ROP of L-lactide.[3] Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine-polylactide(Adn-PLA)conjugates in a simple one-step procedure, without additional catalyst and in the absence of solvent. In this study, computational investigations with density functional theory (DFT) were performed in order to clarify the reaction mechanism leading to the desired Adn-PLA. The results show that a hydrogen bond catalytic mechanism, involving a nucleophilic attack of the activated amine group of adenine onto the carbonyl group of lactide, seem to be plausible.

From the Humpata Plateau to Namibe Desert, SW Angola

After the Congress, a six-day field trip, will be held through three southwestern provinces of Angola (Huíla, Namibe and Cunene), every day starting and ending in the city of Lubango, for overnight stay in Lubango, with the purpose to observe some of the main sites of geological interest in this zone of Angola. The itinerary of this field trip presents the geologic history of Southwestern Angola and its evolution in the scope of the Congo Craton, through a trip that begins in the first excursion days by the oldest geologic formations and phenomena until the recent geologic formations and phenomena on the last excursion days. On the first and second excursion days, September 5th and September 6th, the field trip will go along the Kunene Anorthosite Complex of Angola (KAC), to observe some petrographic features of the KAC that are important to understand the emplacement of this huge igneous massif of the early Kibarean age. These days of the field trip allow the observation of Earthen Construction, because this region of Cunene is privileged to appreciate a kind of Eco-construction, made of raw earth and in wattle and daub, built with ancient techniques, which constitute a real GeoHeritage. On September 7th, in the morning, the destination will be Tundavala, to visit Tundavala Gap, a huge escarpment of more than 1,000 m high cutted in Neo-Archean and Paleo-Proterozoic igneous rocks, the Ruins of Tundavala (quartzite blocks with sedimentary structures) and Tundavala Waterfalls on a quartzitic scarp. After lunch, the field trip continues towards Humpata plateau to observe the panoramic view over Lubango city from the Statue of Cristo Rei, then the outcrops of dolomitic limestones with stromatolites and dolerites and finally the Leba passage, a huge escarpment and one of the most spectacular parts of the Serra da Chela, traversed by a mountain road built in the early 70s of the last century, that can be observed from the belvedere of the Serra da Chela. On September 8th, the destination is the carbonatite complexes of Tchivira and Bonga, belonging to the Mesozoic alkaline massifs of ultrabasic rocks, a rift valley system that occurs during the Early Cretaceous. In this forth excursion day, due to the huge dimensions of these two carbonatite structures it will be visited, only, the Complex of Bonga, namely the outcrops of the northern part of the structure and secondary deposits on the boundary on the southern part of the of the Complex. The last two excursion days, September 9th and September 10th, are to observe the Cretaceous Basin of Namibe. On September 9th, the northern part of Namibe Basin will be visited to observe the volcanic basic rocks of Namibe as well as the interesting paleontological site of Bentiaba. On September 10th, the destination is the southern and more recent part of Namibe Basin, where on the Namib Desert, the exotic plant Welwitschia mirabilis can be observed, as well as Arco, an oasis in the desert. This last excursion day, ends up at the dunes of Tombwa near the mouth of Curoca river and the beautiful bay of Tombwa, where can be observed heavy minerals in their beach sands.