Isothermal Titration Calorimetry of Molecularly Imprinted Polymer Nanospheres

Ultrasensitive isothermal titration calorimetry was used to generate thermodynamic data to assess the binding properties of molecularly imprinted polymer microgels. Microgels were imprinted using L ‐boc‐phenylalanine anilide (L ‐BFA) and then utilized in binding experiments with a variety of probe molecules, structurally closely related to the template molecule. Significant differences were observed between the binding enthalpy of the original template L ‐BFA and those of D ‐BFA, L ‐boc‐phenylalanine, L ‐boc‐tryptophane, and L ‐boc‐tyrosine.     

Ligand‐Dependent Diastereoselectivity in the Palladium‐Catalyzed Copolymerization of Styrene with Carbon Monoxide

[(LL′)Pd(H₂O)](OTf)₂ complexes, in which LL′ is a chelate ligand containing the chiral 4‐benzyl‐4,5‐dihydrooxazole moiety and either pyridin‐2‐yl or 2‐(diphenylphosphino)phenyl substituents, catalyze the copolymerization of styrene with carbon monoxide with an isotactic or prevailingly syndiotactic microstructure, respectively. The chiroptical properties of the copolymers and model studies for carbon monoxide and olefin insertion on related Pd complexes suggest that the reason for the different stereochemistry of the copolymers is a site‐selective coordination of the olefin in the intermediates containing the PN ligand; a lower regioselectivity in the coordination and a different coordination site lead to the different diastereoselectivity for the copolymer formation by the complex containing the NN′‐ligand.     

Preparation of polymers with polycarbonate sequences and their depolymerization; an example of thermodynamic recycling

Initiators based on hydroxytelechelic polyethylene oxide, polytetrahydrofuran and polydimethylsiloxane were used for the anionic ring-opening polymerization of 2.2-dimethyltrimethylene carbonate (DTC). Under suitable conditions high yields of block copolymers of the AB and ABA types were obtained, depending on the initiator used. Ring-closing depolymerization of poly(2.2-dimethyltrimethylene carbonate) [poly(DTC)] and of copolymers containing poly(DTC) blocks with catalysts based on potassium or tin results under suitable conditions in DTC.