Terpenoids, nano-entities and molecular self-assembly

Abstract

Plant metabolites being renewable in nature have tremendous significance for the development of a sustainable society. In this manuscript we show that, terpenoids having nanometric lengths, commonly having several functional groups and several centers of chirality, can be utilized as renewable Molecular Functional Nanos (MFNs). The terpenoids spontaneously self-assembled in liquids yielding different morphologies such as vesicles, tubes, flowers, petals and fibers of nano- to micro-meter dimensions and supramolecular gels. The self-assemblies were utilized for the entrapment and release of fluorophores including anticancer drug, pollutant capture, generation of hybrid materials and catalysis.

A role for terpenoid cyclization in the atom economical polymerization of terpenoids with sulfur to yield durable composites

“…In the course of this work, several cyclization mechanisms for geraniol and farnesol were identified that lead to the incorporation of cyclohexane derivatives into the polymer microstructures. Although such cyclic terpene derivatives are known in biology 49,50 and have been prepared in synthetic small molecule studies, such structures have generally not been invoked as microstructures of terpenoid-derived polymers.…”

Self-assembly of naturally occurring stigmasterol in liquids yielding a fibrillar network and gel

“…The renewable nature of plant metabolites has made them highly signicant in diversied areas of research in chemistry, biology and materials science because their utilizations in science and technology will aid in the development of a sustainable society. [4][5][6] Hierarchical self-assembly yielding supramolecular gels have created a great impact in research in advanced functional materials over the last two decades. [7][8][9][10][11][12][13][14] Such supramolecular gels have found applications in several elds [15][16][17][18] such as sensor devices, 19 thermo-chromic materials, 20 liquid crystals, 21 chemical catalysis, 22 electrically conductive scaffolds, 23,24 templates for cell growth, inorganic structures, 25 cosmetics and food industries.…”

First Vesicular Self‐assembly of a Trihydroxy‐Diterpenoid Andrographolide in Aqueous Medium: Entrapment and Release of Fluorophore and Anti‐Cancer Drug Doxorubicin

“…Self-assembly of amphiphiles with diverse structural features and functional groups has drawn tremendous research interests in the scientific community during the last two decades both for academic reasons as well as for the application of the resulting self-assemblies. [1][2][3][4][5][6][7][8][9][10] Supramolecular architectures like vesicles, micelle, tubes, fiber, rod, helices, etc. are generated by self-assembly of individual components via various types of non-covalent interactions such as H-bonding, electrostatic, van der Waals, aromatic-aromatic interactions, etc.…”

“…Drastic change in the morphology of the self‐assemblies has been observed by minute variation in the backbone and the functional groups present in the molecules. For example, vesicular self‐assembly of triterpenoids arjunolic, maslinic, corosolic, oleanolic and ursolic acids has been obtained in aqueous binary liquid mixtures [3,9,28,29] whereas fibrillar networks and flowers have been obtained from betulin, α‐onocerin, glycyrrhetinic acid [30–32] . Self‐assemblies of the triterpenoids and its derivatives have found interesting applications in the areas of targeted drug delivery, thermochromic materials, liquid crystals, self‐healing hydrogels, chirality imprinting, heterogeneous catalysis, etc [33–40] …”

“…Monoterpenoids (C10) to higher terpenoids (such as C20, C30's) having nanometric lengths with wide range of rigid as well as flexible backbones and different functional groups offer innumerable opportunities as molecular functional nano-entities in diversified areas of modern scientific research. [3] Excellent self-assembly properties of several triterpenoids containing 30 C's such as arjunolic, maslinic, betulinic, olea-nolic, ursolic and glycyrrhetinic acids, α-onocerin, and betulin in different liquids have been reported even without any derivatization. [9,27] Different morphologies such as vesicles, tubes, flowers, sheets and fibrillar networks have been reported by the selfassembly of the triterpenoids.…”