Novel Cationic Amphiphilic Derivatives from Vernonia Oil:  Synthesis and Self-Aggregation into Bilayer Vesicles, Nanoparticles, and DNA Complexants

Abstract

Self-assembling nanostructures were prepared from novel cationic amphiphilic compounds synthesized from vernonia oil, a natural epoxydized triglyceride. The presence of a 12,13-epoxy group on the C18 unsaturated fatty acid, vernolic acid, which is the main constituent of vernonia oil, permitted the synthesis of novel amphiphilic derivatives with a hydrogen-bonding hydroxyl and a cationic headgroup moiety on adjacent carbon atoms. The amphiphiles were prepared in a two-stage synthesis that comprised opening of the epoxy groups with a haloacetic acid, followed by quaternization of the halo group with a tertiary amine containing a C12 aliphatic chain. Intact vernonia oil as the starting material gave a triple-headed cationic amphiphile, containing three vernolic acid derived moieties connected through a glycerol backbone. A single-headed amphiphile with two alkyl chains and a single quaternary ammonium headgroup was synthesized from the methyl ester of vernolic acid as the starting material. The triple-headed derivative could form nonencapsulating structures. Cholesterol was required in the formulation (1:1) to make spherical vesicles that could encapsulate a water-soluble marker. The single-headed derivative, however, formed spherical encapsulating vesicles without cholesterol. TEM, NMR, and FT-IR were used to characterize the vesicles, and molecular structure vs morphology relationships were postulated on the basis of these data. The triple-headed amphiphile also formed a DNA complex that was highly resistant to hydrolysis by DNase. This amphiphile-DNA complex was used as vector for gene transfer in cell culture demonstrating efficient DNA transfection.

Synthesis and characterization of antibacterial polyurethane coatings from quaternary ammonium salts functionalized soybean oil based polyols

“…In this work the QAS was introduced into the polyurethane backbone through acidification of tertiary amine groups of the hard segments (N-methyl diethanol amine) with acetic acid [41,42]. Preparation and application of QAS containing vegetable oils for skin and hair products [43], clay modification [44,45] and drug delivery systems [46][47][48][49] were also considered by researchers. However, a comprehensive survey of literature shows that there is no report regarding preparation and evaluation of antibacterial activity of polyurethanes from vegetable oils containing both QAS and hydroxyl groups.…”

In Silico, In Vitro, and In Vivo Studies Indicate the Potential Use of Bolaamphiphiles for Therapeutic siRNAs Delivery

“…Novel synthetic bolaamphiphiles (bolas) have recently been shown to form complexes with a variety of small and large molecules including peptides, 24,25 proteins, 26 and plasmid DNAs 25,27 delivering them across biological membranes 28 including the blood brain barrier. 18 Bolas also have relatively lower toxicity than cationic liposomes.…”

Triggering RNAi with multifunctional RNA nanoparticles and their delivery

“…We have undertaken to characterize selected RNA carriers both computationally and experimentally. Of special interest to us was a class of lipids called bolaamphiphiles, or bolas, that have been shown to complex with peptides, proteins and plasmid DNAs [135][136][137]. They were also shown to cross cell membranes and are capable of moving across the blood-brain barrier [138].…”