Rethinking Le Corbusier: Urban Design and History

It is generally assumed that Le Corbusier’s urban planning made a break with the past, and that the public spaces designed by him had nothing to do with anything that existed before – a conviction fostered by both the innovative character of his proposals and by the proliferation in his manifestos of watchwords that mask any evocation of the past – words like civilisation machiniste, l’esprit nouveau, l’architecture de demain. However, in his writings, Le Corbusier often mentioned the powerful analogy that exists between the architecture of other times and the logic of modern production. Vers une architecture, for example, contains a mixture of photographs showing silos, cars, aeroplanes, ships (i.e. the fruits of 19th and 20th century civil architecture and mechanical engineering) alongside photographs of Greek and Roman buildings. While Le Corbusier, at the end of the 1920s, claimed “I have only one teacher: the past; only one education: the study of the past”, a series of sketches in the first volume of the Œuvre complète, done during his youth at the archaeological sites visited during his Grand Tour, shows that his interest in the past went far beyond a simple reference.

Journal of Architecture and Urbanism - Rethinking Le Corbusier: Urban Design and History

This is much more than a mere compilation of texts about Corbusian architecture. The articles gathered here focus on Le Corbusier’s reflections about the public space of earlier times and its influence upon his own output, the relationship of his designs with the pre-existing city, and other subjects drawn from all periods of his career and training that clarify the affinity that he established with the past through urban design. They are very heterogeneous, pointing off in different directions and marking the most diverse interests. But at the same time they are interconnected, in that they seek to shed light on the affinity that Le Corbusier established with the past from the point of view of urban design, and open up new perspectives about the public space in his work and its controversial relationship with history. This special issue thus bears witness once again to Le Corbusier’s inexhaustible legacy, but also to the usefulness of research on his work and thought – a subject about which it seemed that everything had already been said when, paradoxically, we now know that there is still almost everything left to say.

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.