Infectious disease is a critically important global healthcare issue. In the U.S. alone there are 2 million new cases of hospital-acquired infections annually leading to 90,000 deaths and 5 billion dollars of added healthcare costs. Couple these numbers with the appearance of new antibiotic resistant bacterial strains and the increasing occurrences of community-type outbreaks, and clearly this is an important problem. Our review attempts to bridge the research areas of natural host defense peptides (HDPs), a component of the innate immune system, and biocidal cationic polymers. Recently discovered peptidomimetics and other synthetic mimics of HDPs, that can be short oligomers as well as polymeric macromolecules, provide a unique link between these two areas. An emerging class of these mimics are the facially amphiphilic polymers that aim to emulate the physicochemical properties of HDPs but take advantage of the synthetic ease of polymers. These mimics have been designed with antimicrobial activity and, importantly, selectivity that rivals natural HDPs. In addition to providing some perspective on HDPs, selective mimics, and biocidal polymers, focus is given to the arsenal of biophysical techniques available to study their mode of action and interactions with phospholipid membranes. The issue of lipid type is highlighted and the important role of negative curvature lipids is illustrated. Finally, materials applications (for instance, in the development of permanently antibacterial surfaces) are discussed as this is an important part of controlling the spread of infectious disease.

In this study, amphiphilic polyoxanorbornene with different quaternary alkyl pyridinium side chains were synthesized. The biological efficiencies of these polymers, with various alkyl substituents, were determined by bacterial growth inhibition assays and hemolytic activity (HC 50 ) against human red blood cells (RBCs) to provide selectivity of these polymers for bacterial over mammalian cells. A series of polymers with different alkyl substituents (ethyl, butyl, hexyl, octyl, decyl and phenylethyl) and two different molecular weights (3 and 10 kDa) were prepared. The impact of alkyl chain length divided the biological activity into two different cases: those with an alkyl substituent containing four or fewer carbons had a minimum inhibitory concentration (MIC) of 200 mg Á mL À1 and a HC 50 greater than 1 650 mg Á mL À1 , while those with six or more carbons had lower MICs 12.5 mg Á mL À1 and HC 50 250 mg Á mL À1 . Using MSI-78, the potent Magainin derivative which has an MIC ¼ 12.0 mg Á mL À1 and HC 50 ¼ 120 mg Á mL À1 , as a comparison, the polymers with alkyl substituents C 4 (four carbons) were not very potent, but did show selectivity values greater than or equal to MSI-78. In contrast, those with alkyl substituents !C 6 were as potent, or more potent, than MSI-78 and in three specific cases demonstrated selectivity values similar to, or better than, MSI-78. To understand if these polymers were membrane active, polymer induced lipid membrane disruption activities were evaluated by dye leakage experiments. Lipid composition and polymer hydrophobicity were found to be important factors for dye release.

A direct comparison of two strategies for designing antimicrobial polymers is presented. Previously, we published several reports on the use of facially amphiphilic (FA) monomers which led to polynorbornenes with excellent antimicrobial activities and selectivities. Our polymers obtained by copolymerization of structurally similar segregated monomers, in which cationic and non-polar moieties reside on separate repeat units, led to polymers with less pronounced activities. A wide range of polymer amphiphilicities was surveyed by pairing a cationic oxanor-bornene with eleven different non-polar monomers and varying the comonomer feed ratios. Their properties were tested using antimicrobial assays and copolymers possessing intermediate hydrophobicities were the most active. Polymer-induced leakage of dye-filled liposomes and microscopy of polymer-treated bacteria support a membrane-based mode of action. From these results there appears to be profound differences in how a polymer made from FA monomers interacts with the phospholipid bilayer compared with copolymers from segregated monomers. We conclude that a well-defined spatial relationship of the whole polymer is crucial to obtain synthetic mimics of antimicrobial peptides (SMAMPs): charged and non-polar moieties need to be balanced locally, for example, at the monomer level, and not just globally. We advocate the use of FA monomers for better control of biological properties. It is expected that this principle will be usefully applied to other backbones such as the polyacrylates, polystyrenes, and non-natural polyamides.

ABSTRACT:In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides. The maleinized soybean oil (SOMA) was then polymerized with diols to the half-ester stage only. Two different types of alcohols was used in this work: (1) short-chain polyhydroxy linear or cyclic alcohols having 2, 3, 4, or 6 hydroxyl groups; and (2) long-chain dihydroxy alcohols. The aim was to determine the effect of functionality and chain length by choosing alcohols with increasing number of hydroxyl groups and different chain lengths. The reaction of alcohols with anhydride functionalized soybean oil to give a polymeric halfester is a reaction that proceeds without the formation of byproducts and is different from complete polyesterification of maleinized oils, which are well known. To improve the reaction yields, different catalysts and different reaction conditions were examined. The structural analysis of the products was done with 1 H-NMR and IR spectroscopy. All of the new polymers obtained were resilient and soft rubbers at room temperature. Castor oil polymer mixed with 60% CaCO 3 and 12% cork powder gave a resilient and nontacky linoleum composition.

ABSTRACT:The Ritter reaction of plant oil triglycerides (such as soybean and sunflower oil) with acrylonitrile was used to introduce acrylamide functionality on the triglyceride. Acrylonitrile and triglycerides were reacted in the presence of H 2 SO 4 , and acrylamide derivatives were obtained in yields of 45 and 50% for sunflower oil and soybean oil, respectively. Radical initiated copolymerization of the acrylamide derivatives of the triglycerides with styrene produced semirigid polymers. Characterization of new monomers and polymers was done by 1 H-NMR, 13 C-NMR, IR, and MS. The swelling behavior of the crosslinked network polymers was determined in different solvents. Glass transiton temperature (T g ) of the cured resin was also determined by differential scanning calorimeter to be 40°C for soybean based polymer and 30°C for sunflower-based polymer. Homo-and copolymerization behavior of acrylamide derivatives of methyl oleate (MOA) and methyl 10-undecenoate (MUA) were also investigated. The reactivity ratios of these monomers with respect to styrene were determined by the Fineman-Ross method using 1 H-NMR spectroscopic data. The reactivity ratios were r sty ϭ 1.776; r moa ϭ 0512 for MOA, and r sty ϭ 1.142; r mua ϭ 0.507 for MUA, respectively. Photopolymerization behaviors of MOA and MUA were also investigated using the photoDSC technique and the rate of polymerization of MUA is higher than that of MOA under the same conditions.

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N-bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, 1 H-NMR, 13C-NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oilstyrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glasstransition temperatures were also determined and soybean oil-based polymer and sunflower oil-based polymer showed a glass transition at 55-65 and 20 -30°C, respectively. The storage moduli of the soybean-based and sunflower-based polymers at room temperature were approximately 1.0 ϫ 10 10 and 1.1 ϫ 10 8 Pa, respectively. Photopolymerization was also carried out by using 2,2-dimethoxy-2-phenyl-acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713-78 and was found to be 5 B at 2.00 mm.

Keywords: Diels-Alder reaction / Cyclization / Methyl calendulate / Methyl α-eleostearate / Maleic anhydride / Renewable feedstockThe thermal, solvent-free addition of maleic anhydride to methyl calendulate (methyl 8,10-trans,12-cis-octadecatrienoate) (1a) occurs with very high regio-and stereoselectivity at C-8 and C-11 of the fatty compound giving the endo-DielsAlder adduct 4 with retention of the cis-configured double bond. Analogously, the Diels-Alder addition of maleic anhydride to methyl α-eleostearate (methyl 9-cis,11,13-trans-octadecatrienoate) (2a) takes place regio-and stereoselectively

ABSTRACT:In this study, methyl oleate was bromoacrylated in the presence of N-bromosuccinimide and acrylic acid in one step. Homopolymers and copolymers of bromoacrylated methyl oleate (BAMO) were synthesized by free radical bulk polymerization and photopolymerization techniques. Azobisisobutyronitrile (AIBN) and 2,2-dimethoxy-2-phenyl-acetophenone were used as initiators. The new monomer BAMO was characterized by FTIR, GC-MS, 1 H, and 13 C-NMR spectroscopy. Styrene (STY), methylmethacrylate (MMA), and vinyl acetate (VA) were used for copolymerization. The polymers synthesized were characterized by FTIR, 1 H-NMR, 13 C-NMR, and differential scanning calorimetry (DSC). Molecular weight and polydispersities of the copolymers were determined by GPC analysis. Ten different feed ratios of the monomers STY and BAMO were used for the calculation of reactivity ratios. The reactivity ratios were determined by the Fineman-Ross and Kelen-Tudos methods using 1 H-NMR spectroscopic data. The reactivity ratios were found to be r sty ϭ 0.891 (FinemanRoss method), 0.859 (Kelen-Tudos method); r bamo ϭ 0.671 (Fineman-Ross method), 0.524 (Kelen-Tudos method).