The copolymerization and terpolymerization of leucine‐N‐carboxyanhydride, β‐benzyl aspartate‐ N‐carboxyanhydride, and valine‐N‐carboxyanhydride in dioxane, initiated with triethylamine, were investigated to determine the random nature of the terpolymer composition for potential applications as targeting drug delivery carriers. 1H NMR was used to obtain the actual monomer compositions of the polymers. The reactivity ratio of each monomer was determined with Fineman–Ross, Kelen–Tüdös, and nonlinear least‐squares curve‐ fitting methods. The product of the estimated reactivity ratios from the monomers in the binary copolymerizations indicated that random polymers were predominantly formed. On the basis of the reactivity ratios determined from the binary copolymers, Alfrey–Goldfinger equations were used to estimate the compositions of the terpolymers. There was no statistical difference between the actual monomer compositions and the calculated compositions of the terpolymers; this validated the reactivity ratios estimated by Fineman–Ross, Kelen–Tüdös, and nonlinear least‐squares curve‐ fitting methods. Therefore, the poly(leucine‐β‐Bzl‐ aspartate‐valine) synthesized in this study was primarily a random terpolymer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 317–325, 2004

[reaction: see text] Synthesis of glycosyl cyanides was optimized with a new catalyst system. Reduction of tri-O-acetyl-beta-L-fucopyranosyl cyanide with Pd-hydrogen, in the presence of Ac(2)O and Boc(2)O, gave N-protected-mono- and -di-(2,3,4-tri-O-acetyl-beta-L-fucopyranosylmethyl)-amines, which allow for the syntheses of small cluster oligosaccharide mimetics of fucopyranosylomethyl-substituted ureas. From di-(2,3,4-tri-O-acetyl-beta-L-fucopyranosylmethyl) amine was also prepared a carbamoyl chloride as a potentially useful synthon for preparation of more complex C-glycosidic conjugates.

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Three different characterization methods-13 C NMR spectroscopy, a terminal terpolymerization model, and a probability analysis based on the Poisson distribution-were used to determine the microstructure of random terpolymers. The methods were used to determine the amino acid sequence distribution of random terpolymers prepared from the polymerization of N-carboxyanhydrides that contained L-leucine, b-benzyl-L-aspartate, and L-valine. Poly(L-leucine-L-aspartic acid-L-valine) [poly(LDV)] was designed as a target specific substrate for the a 4 b 1 integrin that recognizes the tripeptide sequence leucine-aspartic acid-valine (LDV). The presence of the tripeptide sequence LDV within the polymer was determined to be eight LDV triad sequences on average in terpolymers of approximately 100 kDa.