A supramolecular electrochemical probe based on a tetrazole derivative pillar[5]arene/methylene blue system.

For the first time, an original synthetic approach has been developed that enables the introduce ten tetrazole fragments into the pillar[5]arene structure. A supramolecular electrochemical probe was assembled for the first time from the obtained macrocycles and an electrochemically active signal converter: methylene blue (MB) dye. The ability of pillar[5]arene containing tetrazole fragments to selectively bind MB was confirmed by UV-vis and 2D H-H NOESY spectroscopy.

Antibacterial Activity of Various Morphologies of Films Based on Guanidine Derivatives of Pillar[5]arene: Influence of the Nature of One Substitute on Self-assembly.

The progress of the pillar[5]arene chemistry allowed us to set out a new concept on application of the supramolecular assemblies to create antimicrobial films with variable surface morphologies and biological activities. Antibacterial films were derived from the substituted pillar[5]arenes containing nine pharmacophoric guanidine fragments and one thioalkyl substituent. Changing the only thioalkyl fragment in the macrocycle structure made it possible to control the biological activity of the resulting antibacterial coating.

The Synthesis and Antibacterial Properties of Pillar[5]arene with Streptocide Fragments.

The growing problem of bacterial resistance to antimicrobials actualizes the development of new approaches to solve this challenge. Supramolecular chemistry tools can overcome the limited bacterial resistance and side effects of classical sulfonamides that hinder their use in therapy. Here, we synthesized a number of pillar[5]arenes functionalized with different substituents, determined their ability to self-association using DLS, and characterized antimicrobial properties against , , , , via a resazurin test.

Towards potential antifungal agents: synthesis, supramolecular self-assembly and activity of azole mono-, sesqui- and diterpenoids.

Terpenes and their derivatives are natural antifungal and antimicrobial agents. In this paper, potential antifungal agents were developed on the basis of farnesol, geraniol, myrtenol, perillyl alcohol, cedrol and phytol. The synthesized compounds exist in aqueous solutions as stable associates ( = 142-216 nm, PDI 0.

Toward Pathogenic Biofilm Suppressors: Synthesis of Amino Derivatives of Pillar[5]arene and Supramolecular Assembly with DNA.

New amino derivatives of pillar[5]arene were obtained in three stages with good yields. It was shown that pillar[5]arene containing thiaether and tertiary amino groups formed supramolecular complexes with low molecular weight model DNA. Pillar[5]arene formed complexes with a DNA nucleotide pair at a ratio of 1:2 (macrocycle/DNA base pairs), as demonstrated by UV-visible and fluorescence spectroscopy.

Fluorescein-Labeled Thiacalix[4]arenes as Potential Theranostic Molecules: Synthesis, Self-Association, and Antitumor Activity.

In this paper, a series of thiacalix[4]arenes were synthesized as potential theranostic molecules for antitumor therapy. We propose an original strategy for the regioselective functionalization of thiacalix[4]arene with a fluorescent label to obtain antiangiogenic agent mimetics. The aggregation properties of the synthesized compounds were determined using the dynamic light scattering.

Self-Healing Thiolated Pillar[5]arene Films Containing Moxifloxacin Suppress the Development of Bacterial Biofilms.

Polymer self-healing films containing fragments of pillar[5]arene were obtained for the first time using thiol/disulfide redox cross-linking. These films were characterized by thermogravimetric analysis and differential scanning calorimetry, FTIR spectroscopy, and electron microscopy. The films demonstrated the ability to self-heal through the action of atmospheric oxygen.

Water-soluble pillar[5]arene sulfo-derivatives self-assemble into biocompatible nanosystems to stabilize therapeutic proteins.

Pillar[5]arenes containing sulfonate fragments have been shown to form supramolecular complexes with therapeutic proteins to facilitate targeted transport with an increased duration of action and enhanced bioavailability. Regioselective synthesis was used to obtain a water-soluble pillar[5]arene containing the fluorescent label FITC and nine sulfoethoxy fragments. The pillar[5]arene formed complexes with the therapeutic proteins binase, bleomycin, and lysozyme in a 1:2 ratio as demonstrated by UV-vis and fluorescence spectroscopy.

Supramolecular Amphiphiles Based on Pillar[5]arene and Meroterpenoids: Synthesis, Self-Association and Interaction with Floxuridine.

In recent years, meroterpenoids have found wide biomedical application due to their synthetic availability, low toxicity, and biocompatibility. However, these compounds are not used in targeted drug delivery systems due to their high affinity for cell membranes, both healthy and in cancer cells. Using the approach of creating supramolecular amphiphiles, we have developed self-assembling systems based on water-soluble pillar[5]arene and synthetic meroterpenoids containing geraniol, myrtenol, farnesol, and phytol fragments.

Towards Universal Stimuli-Responsive Drug Delivery Systems: Pillar[5]arenes Synthesis and Self-Assembly into Nanocontainers with Tetrazole Polymers.

In this work, we have proposed a novel universal stimulus-sensitive nanosized polymer system based on decasubstituted macrocyclic structures-pillar[5]arenes and tetrazole-containing polymers. Decasubstituted pillar[5]arenes containing a large, good leaving tosylate, and phthalimide groups were first synthesized and characterized. Pillar[5]arenes containing primary and tertiary amino groups, capable of interacting with tetrazole-containing polymers, were obtained with high yield by removing the tosylate and phthalimide protection.

Metallo-Supramolecular Coordination Polymers Based on Amidopyridine Derivatives of Pillar[5]arene and Cu(II) and Pd(II) Cations: Synthesis and Recognition of Nitroaromatic Compounds.

Decasubstituted pillar[5]arenes containing amidopyridine fragments have been synthesized for the first time. As was shown by UV-vis spectroscopy, the pillar[5]arenes with -amidopyridine fragments form supramolecular associates with Cu(II) and Pd(II) cations in methanol in a 2:1 ratio. Using a sol-gel approach these associates are transformed into metallo-supramolecular coordination polymers (supramolecular gels) which were characterized as amorphous powders by scanning electron microscopy (SEM) and dynamic light scattering (DLS).

Progress in the Chemistry of Macrocyclic Meroterpenoids.

In the last decade, the chemistry of meroterpenoids-conjugated molecules formed from isoprenyl fragments through biosynthetic pathways-has developed rapidly. The class includes some natural metabolites and fully synthetic fragments formed through nonbiological synthesis. In the field of synthetic receptors, a range of structures can be achieved by combining fragments of different classes of organic compounds into one hybrid macrocyclic platform which retains the properties of these fragments.

Antimicrobial Activity of Calixarenes and Related Macrocycles.

Calixarenes and related macrocycles have been shown to have antimicrobial effects since the 1950s. This review highlights the antimicrobial properties of almost 200 calixarenes, resorcinarenes, and pillararenes acting as prodrugs, drug delivery agents, and inhibitors of biofilm formation. A particularly important development in recent years has been the use of macrocycles with substituents terminating in sugars as biofilm inhibitors through their interactions with lectins.

Self-Assembly of Supramolecular Architectures by the Effect of Amino Acid Residues of Quaternary Ammonium Pillar[5]arenes.

Novel water-soluble multifunctional pillar[]arenes containing amide-ammonium-amino acid moiety were synthesized. The compounds demonstrated a superior ability to bind (1S)-(+)-10-camphorsulfonic acid (-CSA) and methyl orange dye depending on the nature of the substituent, resulting in the formation one-to-one complexes with both guests. The formation of host-guest complexes was confirmed by ultraviolet (UV), circular dichroism (CD) and H NMR spectroscopy.

Nanostructured Polyelectrolyte Complexes Based on Water-Soluble Thiacalix[4]Arene and Pillar[5]Arene: Self-Assembly in Micelleplexes and Polyplexes at Packaging DNA.

Controlling the self-assembly of polyfunctional compounds in interpolyelectrolyte aggregates is an extremely challenging task. The use of macrocyclic compounds offers new opportunities in design of a new generation of mixed nanoparticles. This approach allows creating aggregates with multivalent molecular recognition, improved binding efficiency and selectivity.

Towards new nanoporous biomaterials: self-assembly of sulfopillar[5]arenes with vitamin D into supramolecular polymers.

Novel water-soluble, deca-substituted pillar[5]arenes containing thiasulfate and thiacarboxylate fragments were synthesized and characterized. UV-vis, 2D 1H-1H NOESY and DOSY NMR spectroscopy revealed the ability of pillar[5]arenes containing thiasulfate fragments to form an inclusion complex with cholecalciferol (vitamin D3) in a 1 : 2 ratio (lg Kass = 2.2).

Nanoparticles based on the zwitterionic pillar[5]arene and Ag: synthesis, self-assembly and cytotoxicity in the human lung cancer cell line A549.

For the first time, stable pillar[5]arene/Ag nanoparticles, consisting of water-soluble pillar[5]arene containing γ-sulfobetaine fragments and Ag ions without Ag-Ag bonds, were synthesized and characterized. The pillar[5]arene/Ag (ratio 1:10) nanoparticles obtained were cubic with a rib length of 100 nm and are less cytotoxic than Ag ions. The survival of the A549 model cells in the presence of pillar[5]arene/Ag (1:10) nanoparticles at a concentration of 30 and 40 μM was 76% and 55%, while in the absence of pillar[5]arene, the cell survival for free Ag ions at the same concentration was 30% and 10%, respectively.

Supramolecular neuromuscular blocker inhibition by a pillar[5]arene through aqueous inclusion of rocuronium bromide.

A water-soluble pillar[5]arene, decafunctionalized with thioether and carboxylate fragments, was synthesized as a structural analogue of Sugammadex. Its ability to restore the contraction of the diaphragm muscle by encapsulating the muscle relaxant rocuronium bromide was demonstrated. Using UV-vis, NMR and fluorescence spectroscopy, it was shown that the muscle relaxant is associated with the pillar[5]arene with an association constant of 4500 M-1 and a stoichiometry of 1 : 1.

Synthesis of Tris-pillar[5]arene and Its Association with Phenothiazine Dye: Colorimetric Recognition of Anions.

A multicyclophane with a core based on tris(2-aminoethyl)amine (TREN) linked by amide spacers to three fragments of pillar[5]arene was synthesized. The choice of the tris-amide core allowed the multicyclophane to bind to anion guests. The presence of three terminal pillar[5]arene units provides the possibility of effectively binding the colorimetric probe -phenyl-3-(phenylimino)-3H-phenothiazin-7-amine ().

Synthesis of Water-Soluble Amino Functionalized Multithiacalix[4]arene via Quaternization of Tertiary Amino Groups.

A convenient approach to the synthesis of multithiacalix[4]arene derivatives containing amino groups and phthalimide fragments by the formation of quaternary ammonium salts is presented. As the initial macrocycle for the synthesis of multithiacalix[4]arenes, a differently substituted butylthiacalix[4]arene containing bromoacetamide and three phthalimide fragments was used in a conformation. The macrocycle in conformation containing the tertiary amino groups was found to be a convenient core for the multithiacalix[4]arene systems.