Polycondensations of hydroxycarboxylic acids derived from optically active aminoalcohols and acid anhydrides—syntheses of functional poly(ester-amide)s

Syntheses and polycondensations of optically active hydroxycarboxylic acids prepared from acid anhydrides and aminoalcohols were carried out. Novel polymers with M̄_n 9900–27,200 were obtained by the polycondensations of hydroxycaboxylic acids derived from maleic or succinic acid using 1.2 eq. of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl) in DMF (2M) at room temperature for 8 h in satisfactory yields. Meanwhile, a hydroxycarboxylic acid obtained from phthalic acid afforded no polymer but a phthalimide derivative. The radical additions of ethanethiol or mercaptoethanol with the polymers derived from maleic anhydride proceeded smoothly in satisfactory incorporation ratios (65–98%), respectively. The polymer obtained from succinic anhydride and 2-aminoethanol showed hydrolytic degradability. © 1997 John Wiley & Sons, Inc.     

Synthesis and radical polymerization of 2-vinyldibenzothiophene

A monomer having dibenzothiophene moiety, 2-vinyldibenzothiophene (1), was prepared by the Ni-catalyzed cross-coupling reaction of vinyl bromide with the Grignard reagent of 2-bromodibenzothiophene. The radical homopolymerization of 1 and the copolymerization with styrene were carried out at 60°C in toluene (1.0M) for 20 h using AIBN (5 mol %) as an initiator to obtain the corresponding polymers in high yields. Thermal analyses of the copolymers showed that both 10% weight loss and glass transition temperatures increase when increasing the content of 1 unit. The monomer reactivity ratio was evaluated as r₁ = 2.55 (1) and r₂ = 0.16 (styrene). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2813–2819, 1997     

Syntheses and radical polymerizations of optically active (meth)acrylamides having amino acid moieties

Syntheses and radical polymerizations of several (meth)acrylamides having L -amino acid moieties were examined. The monomers were prepared by the reactions of L -amino acid ester hydrochlorides with (meth)acryloyl chloride in the presence of triethylamine in satisfactory yields. Radical polymerizations of the monomers were carried out in the presence of AIBN (1 mol %) in bulk and in several solvents to afford the corresponding polymers in satisfactory yield. The glass transition temperatures and specific rotations of the polymers depended on the substituents of the L -amino acid moieties. Nearly the same specific rotations were observed for the monomers and the model compounds of the polymer units, N-pivaloyl amino acid methyl esters. On the contrary, the specific rotations of the polymers shifted to the negative direction in ca. 30°. The interaction between the polymer side chains might affect the changes in the specific rotations from monomers to polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2619–2629, 1997     

Strain-Induced “Band Flips” in Cyclodecaamylose and Higher Homologues

The cavity of the larger molecule has less space for guests! Unlike the structure of the smaller annular cyclodextrins, that of the higher homologues of cycloamyloses (CAs) with more than ten glucose units contains a 90° kink between adjacent glucose residues within one half of the molecule and a 180° band flip between adjacent units in different halves (see depicted section of the CA14 structure) to yield butterfly-shaped structures with narrow, groovelike cavities.     

A Fullerene/Lipid Electrode Device: Reversible Electron Transfer Reaction of C60 Embedded in a Cast Film of an Artificial Ammonium Lipid on an Electrode in Aqueous Solution

Two reversible one-electron transfers are observed for an electrode device made from C₆₀ and an artificial lipid (see schematic drawing). Cyclic voltammetric studies reveal that the redox couples are unchanged even after 50 cycles, thus indicating that the C₆₀ radical monoanion and the C₆₀ dianion generated in aqueous solution are very stable.     

Synthesis and reactions of a poly(methacrylate) from an optically active amino alcohol

Synthesis and radical polymerization of a novel optically active methacrylate, (S)–2–tert–butoxycarbonylamino–3–phenylpropyl methacrylate (MA–F–BOC), were examined. MA–F–BOC was synthesized from methacrylic acid and N–protected (L)–phenylalaninol. Radical polymerization of MA–F–BOC quantitatively afforded the corresponding polymethacrylate with a relatively high molecular weight. Radical copolymerizations of MA–F–BOC were carried out with styrene and acrylamide to afford the copolymers. Radical polymerization of MA–F–BOC in the presence of n–butanethiol afforded the oligomers, whose degrees of polymerizations were 3.3–8.0. The BOC group was completely cloven with HBr to afford the corresponding optically active polymeric amine quantitatively. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 1981–1986, 1998     

Novel lipase-catalyzed ring-opening copolymerization of oxiranes and succinic anhydride forming polyesters bearing functional groups

Oxiranes, such as glycidyl phenyl ether (GPE) and benzyl glycidate (BG), were copolymerized with succinic anhydride (SA) by lipase at a temperature between 60 and 80°C to yield the corresponding polyesters bearing carboxyl or phenyl groups. Bulk polymerization, especially at the temperature of 80°C, and preferably using porcine pancreatic lipase gave biodegradable polyesters with a molecular weight greater than 5000.