All reagents and solvents were purchased from Aldrich Chemical Co. and used as received. Benzoxazine 1 was prepared according to the reported procedure, 5c and the purity is >95% as determined by 1 H NMR.Measurements. 1 H NMR spectra were taken on a Bruker AM-360 (360 MHz). Chemical shifts were reported in parts per million relative to TMS as an internal standard (δ TMS = 0) for 1 H NMR spectra. The solvent for NMR measurement was deuterated DMSO or deuterated chloroform. DSC studies were done on a DSC-Q20 thermal analyzer from TA Instruments with N 2 as a purge gas at a scanning rate of 10 °C/min. About 5 mg of samples was tested in high-pressure closed aluminum pans.General Procedures for Ring-Opening Polymerization of Benzoxazine 1. In a test tube, benzoxazine 1 (113 mg, 0.5 mmol) and a catalyst (1 or 5 mol %) were dissolved in acetone (∼0.2 mL). The mixture was dried at room temperature under high vacuum for ∼1 h and heated under the conditions showed above. Then the resulting mixture was subjected to routine analysis.
Functions similar to those of catalytic antibodies are shown by molecularly imprinted polymers, when the cavities in the polymer not only have the correct form but also contain catalytically active groups. Polymers have now been prepared by imprinting with a transition state analogue of alkaline ester hydrolysis (see picture). These “artificial enzymes” combine strong catalytic activity with typical enzyme properties such as Michaelis—Menten kinetics, competitive inhibition, turnover, and substrate selectivity.
Wie katalytische Antikörper, können molekular geprägte Polymere fungieren, wenn die Hohlräume im Polymer nicht nur die richtige Form haben, sondern auch noch katalytisch wirksame Gruppen enthalten. Es ist jetzt gelungen, für die basenkatalysierte Esterhydrolyse geprägte Polymere herzustellen (siehe Bild), die typische Eigenschaften wie Michaelis‐Menten‐Kinetik, kompetitive Hemmung, Turnover und Selektivität mit guter katalytischer Aktivität verbinden.magnified image
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