Diastereoselective intramolecular cyclization/Povarov reaction cascade for the one-pot synthesis of polycyclic quinolines.

The method for the synthesis of complex alkaloid-like aza-heterocycles has been developed through the Povarov reaction of in situ generated 2-oxoimidazolium cations. The reaction lead to the formation of 2 C-N, 2 C-C bonds and three stereocentres, and features excellent regio- and diastereoselectivity. Based on the controlled experiments and quantum chemistry data, the mechanism of the reaction cyclization was proposed and diastereoselectivity origins were rationalized. Additionally, a straightforward synthesis of hardly accessible 4,4'-bi(imidazol-2-one) derivatives has been achieved using the same methodology.

Thiacalixarene based quaternary ammonium salts as promising antibacterial agents.

The search for new antibacterial and antiseptic drugs is an urgent problem due to the resistance of microorganisms to existing drugs. In this work, for the first time, the design of antibacterial and bactericidal agents based on quaternary ammonium compounds on thiacalixarene macrocyclic platform was proposed and implemented. A series of tetrasubstituted quaternary ammonium salts with different nature and length of the substituent (-N+(CH3)2R, R = CH2Ph, CnH2n+1, n = 1, 4, 8, 10) based on p-tert-butylthiacalix[4]arene in cone and 1,3-alternate conformations was obtained with excellent yields. The obtained compounds have a high antibacterial effect against Gram-positive (S. aureus, S. epidermidis, B. subtilis) bacteria comparable with commercial antiseptics chlorhexidine, miramistin and benzalkonium chloride. It was found that quaternary ammonium derivatives of thiacalix[4]arene in 1,3-alternate conformation more effectively inhibit the growth of the tested bacterial strains in comparison with compounds in cone conformation. Cytotoxicity studies on human skin fibroblast (HSF) cells demonstrated that all compounds were less toxic compared to reference drugs. The different type of interaction of the studied compounds with model DPPC lipid membranes explains different antibacterial activity and cytotoxicity of compounds. The compounds in cone conformation are adsorbed on the DPPC vesicles membrane surface, while the incorporation of lipophilic alkyl fragments of macrocycles in 1,3-alternate conformation into the membrane leads to "clumping" of DPPC vesicles. It was shown the saving of antibacterial activity of thiacalixarene derivatives in 1,3-alternate conformation on Gram-positive clinical strains. The obtained results allow viewing the described thiacalixarene based quaternary ammonium compounds as promising molecules in the development of the new antibacterial agents.

Highly selective binding of methyl orange dye by cationic water-soluble pillar[5]arenes.

A new water-soluble pillar[5]arene with an amide fragment and triethylammonium groups was synthesized by our original method of aminolysis of the ester groups. Using UV-spectroscopy, it is shown that cationic pillar[5]arenes are able to selectively form 1 : 1 complexes with some hydrophobic anions: the guests with bulky uncharged or negatively charged substituents hindering entry into the macrocycle cavity. Highly selective binding of the most lipophilic guest, methyl orange dye, in the form of organic anion salts by positively charged water-soluble pillar[5]arenes was detected. In the case of the azo dye the appropriate Kass values were 10-100-fold higher than those calculated for the other sulfonic acid derivatives studied. The 2D NMR NOESY (1)H-(1)H spectroscopy confirms the formation of the inclusion complex: negative charge sulfonate head is outside the cavity of pillar[5]arenes and the hydrophobic fragment of the guest is located in the cavity.

Twice as smart behavior of tert-butylthiacalix[4]arene derivative in glassy and crystalline form.

A studied tert-butylthiacalix[4]arene derivative with four N-(2-acetoxyethyl)carbamoylmethoxy substituents on its lower rim in partial-cone configuration (calixarene 1) can remember its previous treatment in three essentially different ways by the formation either of a molecular glass or two metastable polymorphs after heating or the removal of an included guest molecule. Guest-induced memory is very selective with a polymorph created only after the release of a few included guests among a large series of those studied and is detected via an exothermic transition. Along with ordinary properties, like glass transition, curing and cold crystallization, the molecular glass from 1 is selective due to its ability to crystallize in solvent vapors and vapor mixtures over a well-defined concentration range. Being cooperative, this property may be used for the visual detection of ethanol content in water solution when it reaches a threshold value.

Amide-functionalized pillar[5]arenes as a novel class of macrocyclic receptors for the sensing of H2PO4- anion.

A novel class of amide-functionalized pillar[5]arenes, that is, alkyl and aryl amide derivatives, has been synthesized. Highly selective binding of the dihydrogen phosphate anion over a range of anions by the new synthetic receptors is reported. First, the "binding strength-selectivity" relationship has been decided for the pillar[5]arene/anion systems.

Discrimination of apple juice and herbal liqueur brands with solid-state electrodes covered with polyaniline and thiacalixarenes.

Solid-contact ion-selective electrodes based on glassy carbon electrode covered with electropolymerized polyaniline and tetrasubstituted thiacalix[4]arene ionophores with hexyl and o-pyridylamido functional groups at the lower rim have been developed and examined in the discrimination of the brands of apple juices and herbal liqueurs. For this purpose, the liquids tested were diluted and spiked with a constant amount of Fe(3+) ions. The variation of the signal toward Fe(3+) ions was achieved due to their involvement in the reactions with the organic ligands and the antioxidants present. As was shown, the combination of the three electrodes with various receptors makes it possible to predict the brand of apple juices and herbal liqueurs using linear discriminant analysis in 95-100% cases. The discrimination procedure makes it possible to discriminate liquids within 20 min. Besides, the electrodes developed make it possible to detect individual antioxidants (ascorbic, malic, oxalic acids, hydroquinone, and quercetin) in the range from 5.0x10(-6) to 1.0x10(-2) M in direct potentiometric measurements and redox titration.

Selectivity of solid-contact Ag potentiometric sensors based on thiacalix[4]arene derivatives.

Potentiometric sensors based on glassy carbon electrode covered with polyaniline and thiacalix[4]arenes containing amidopyridine, morpholide, pyrrolidide and hydrazide functional groups in cone, partial cone and 1,3-alternate conformations have been developed and applied for determination of Ag(+) ions in the range from 1.0 x 10(-2) to 4.0 x 10(-7)M and limits of detection from 1 x 10(-7) to 3.5 x 10(-8)M. The sensitivity of Ag(+) detection decreases in the following range of thiacalix[4]arene substituents: morpholide>pyrrolidide>amidopyridine>hydrazide. Potentiometric selectivity coefficients predominantly showed binding of Ag(+), Hg(II) and Fe(III) ions over other transient and alkali metals. The influence of functional groups and conformation of receptor on the selectivity of the sensor response was investigated. As shown, selectivity and sensitivity of Ag(+) determination depends on the steric accessibility of the binding site and flexibility of the receptor structure. For Fe(III) ions, changes of the sensor potential are also determined by their implementation in redox reactions of polyaniline.

Ag selective electrode based on glassy carbon electrode covered with polyaniline and thiacalix[4]arene as neutral carrier.

Potentiometric sensor based on glassy carbon electrode covered with polyaniline and neutral carrier, e.g. thiacalix[4]arene containing pyridine fragments in the substituents in the lower rim has been developed and applied for determination of Ag(+) ions in the range from 1.0x10(-2) to 5.0x10(-7)M with the response time of 12s. The presence of thiacalixarene in the surface layer improves the reversibility and selectivity of the signal towards transient metal ions. The potentiometric selectivity coefficients were determined for various measurement conditions. As shown, the pH control and the use of NaF as a masking agent fully eliminate the interfering effect of Hg(2+) and Fe(3+) ions, respectively. The reaction of Ag(+) with thiacalixarene was proved by the investigation of the extraction of picrate complexes of transient metals in the organic phase. The potentiometric sensor developed was successfully used for the potentiometric determination of silver sulfathiazole (Argosulfantrade mark).