Polyurethane cationomers. I. Structure–properties relationships

Polyurethane (PU) cationomers have been synthesized by quaternizing tertiary amine-containing linear polyurethanes using different quaternizers containing acid groups. The effect of chemical structure of PU cationomers on the physical properties was studied. The mechanical properties of PU cationomers were improved with decreasing molecular weight of poly(caprolactone) glycol, and increasing concentration of quaternary ammonium. Decreasing the carbon number in the alkyl group of the N-alkyl diethanol-amine chain-extenders, and using rigid symmetrical diisocyanates, the mechanical properties of the PU cationomers were increased. The effects of these factors on the glass transition temperature of PU cationomers were also examined. The mechanical properties of the PU cationomers decreased by immersion in water and recovered after removal of the water.     

Halogenation of 2-Hydroxynicotinic Acid

A convenient method to prepare 5-halo-2-hydroxy-nicotinic acid is described.     

Synthesis and Crystal Structure of 4,4′‐(Methylenediimino)bis‐1,2,5‐Oxadiazole‐3‐carboxylic Acid and Carboxamide

4,4′‐(Methylenediimino)bis‐1,2,5‐oxadiazole‐3‐carboxylic acid and 4,4′‐(methylenediimino)bis‐1,2,5‐oxadiazole‐3‐carboxamide have been synthesized by the acid‐catalyzed condensation of 4‐amino‐1,2,5‐oxadiazole‐3‐carboxylic acid and 4‐amino‐1,2,5‐oxadiazole‐3‐carboxamide with formaldehyde. The crystal and molecular structures of the compounds have been determined by X‐ray crystallography. 4,4′‐(Methylenediimino)bis‐1,2,5‐oxadiazole‐3‐carboxylic acid crystallizes in space group C2/c, and its measured density is 1.800 g/mL, significantly above the calculated value of 1.68 g/mL. 4,4′‐(Methylenediimino)bis‐1,2,5‐oxadiazole‐3‐carboxamide crystallizes in space group P2₁/c, and its measured density is 1.623 g/mL, in close agreement with the calculated value of 1.64 g/mL. The structure of the starting amide 4‐amino‐1,2,5‐oxadiazole‐3‐carboxamide has also been determined. These data, combined with literature data, suggest that ortho‐aminocarboxylic acids have unusually high densities, but the reasons for this are unclear.     

Synthesis and characterization of interpenetrating polymer networks with nonlinear optical properties

We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one T_g, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc.     

Spectroscopic studies of the stability of monolayers of 2-docosylamino-5-nitropyridine at the air/water interface

Monolayers of 2-docosylamino-5-nitropyridine (DCANP) at the air/water interface were investigated by UV/Vis spectroscopy. The combination of this method with the classic constant-area relaxation technique yields insight into the longtime stability and the collapse behavior of monolayers. We have demonstrated that monolayers of DCANP are certainly stable under standard deposition conditions. At surface pressures above 20 mN/m monolayer instabilities lead to the formation of a three-dimensional head-to-head multilayered structure.     

Growth of hexagonal quantum dots under preferential evaporation

We perform numerical simulations of hexagonal quantum dots of AlGaN semiconductors. We show that the competition between surface mass diffusion and evaporation rules the morphology of the quantum dots. The system displays three different behaviors: presence of separated islands without a wetting layer, islands dissolving into the wetting layer, or islands that do not evolve. The first behavior is of special interest because its optoelectrical properties are significantly improved in comparison with quantum dots with a wetting layer.     

Interpenetrating polymer networks from polyurethanes and methacrylate polymers. I. Effect of molecular weight of polyols and NCO/OH ratio of urethane prepolymers on properties and morphology of IPNs

Two types of reinforced elastomeric interpentrating polymer network (IPN) were prepared by simultaneous polymerization and crosslinking in solution. The first type consisted of polyurethane-poly(methyl methacrylate) (PU/PMMA), and the second, of polyurethane-poly(methyl methacrylate-methacrylic acid) PU/P(MMA–MAA) of constant composition (90/10) and (80/20) by weight, respectively. The members of each type differed in the NCO/OH ratio of the PU prepolymer and the molecular weight (MW) of the polyol in the PU component because we wished to investigate systematically the effect of changing the NCO/OH ratio and MW of the polyol on the mechanical properties and morphology of the resulting IPNs. The mechanical properties, particularly the modulus of both tyes of IPN, increased with increasing NCO/OH ratio and decreased with increasing MW of the polyol in the PU. The morphology of the IPNs was studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Improved phase compatibility and decreasing extent of phase separation was observed in both types of IPN with increasing NCO/OH ratio and decreasing MW of the polyol used in the PU. These results may imply that improved interpenetration results from increasing the NCO/OH ratio and decreasing the MW of the polyol in the PU component. The fact that the effect is more pronounced with the type of PU-P(MMA–MAA) IPN can be rationalized as due to the additional hydrogen bonding between the carbonyl in the carboxyl groups and the urethane or urea groups in the PU component.     

Design of Oligourea-Based Foldamers with Antibacterial and Antifungal Activities

There is an urgent need to develop new therapeutic strategies to fight the emergence of multidrug resistant bacteria. Many antimicrobial peptides (AMPs) have been identified and characterized, but clinical translation has been limited partly due to their structural instability and degradability in physiological environments. The use of unnatural backbones leading to foldamers can generate peptidomimetics with improved properties and conformational stability. We recently reported the successful design of urea-based eukaryotic cell-penetrating foldamers (CPFs). Since cell-penetrating peptides and AMPs generally share many common features, we prepared new sequences derived from CPFs by varying the distribution of histidine- and arginine-type residues at the surface of the oligourea helix, and evaluated their activity on both Gram-positive and Gram-negative bacteria as well as on fungi. In addition, we prepared and tested new amphiphilic block cofoldamers consisting of an oligourea and a peptide segment whereby polar and charged residues are located in the peptide segment and more hydrophobic residues in the oligourea segment. Several foldamer sequences were found to display potent antibacterial activities even in the presence of 50% serum. Importantly, we show that these urea-based foldamers also possess promising antifungal properties.