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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 1 H- 1 H NOESY spectroscopy. The stoichiometry of the resulting pillar[5]arene/MB complex = 1 : 2. This new supramolecular probe pillar[5]arene/MB allowed the detection of changes in the electrochemical signals of MB implemented in the supramolecular complex depending on the presence or absence of some metal ions (Zn 2+ and Co 2+ ) that do not exert their own redox activity. This will find further applications for the enhancement of the range of analytes detected by their influence on host-guest complexation and for the design of biosensors based on specific DNA-MB interactions.

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. Pretreatment of the surface with aqueous solution of the amphiphilic pillar[5]arenes reduced the biofilm thickness by 56 ± 10% of Gram-positive Staphylococcus aureus in the case of the pillar[5]arene containing a thiooctyl fragment and by 52 ± 7% for the biofilm of Gram-negative Klebsiella pneumoniae in the case of pillar[5]arene containing a thiooctadecyl fragment. Meanwhile, the cytotoxicity of the synthesized macrocycles was examined at a concentration of 50 μg/mL, which was significantly lower than that of bis-guanidine-based antimicrobial preparations.

The development of adsorbents with robust molecular discrimination capabilities for halogenated organic compounds (HOCs) holds significant importance due to their potential in adsorptive separation and mitigation of associated health risks. In this study, we report a molecular discrimination behavior based on crystalline hybrid macrocyclic arene H , offering precise capture of cis - trans isomers and length-selective separation of HOCs. The activated H crystals ( H α) demonstrate exceptional discrimination and separation performance by selectively capturing trans -1,2-dichloroethylene ( trans -DCE ) from cis / trans -isomer mixtures with a high selectivity of 98.8%. Evidenced by single-crystal X-ray diffraction and density functional theory (DFT) calculations, this high adsorption selectivity arises from the formation of more stable complex crystals between H and the preferred guest trans -DCE . Moreover, H α exhibits the ability to selectively trap size-matched 1,2-dibromoethane ( DBE ) from mixtures of alkylene dibromides with varying alkane-chain lengths, although their capture and separation are recognized to be difficult as a consequence of low-polarity bonds. The solid-state transformations between guest-free and guest-containing H α crystals indicate their recyclability, showcasing promising prospects for potential applications.

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. The association constants of pillar[5]arene with DNA were lgKass1:1 = 2.38 and lgKass1:2 = 5.07, accordingly. By using dynamic light scattering and transmission electron microscopy, it was established that the interaction of pillar[5]arene containing thiaether and tertiary amino groups (concentration of 10-5 M) with a model nucleic acid led to the formation of stable nanosized macrocycle/DNA associates with an average particle size of 220 nm. It was shown that the obtained compounds did not exhibit a pronounced toxicity toward human adenocarcinoma cells (A549) and bovine lung epithelial cells (LECs). The hypothesis about a possible usage of the synthesized macrocycle for the aggregation of extracellular bacterial DNA in a biofilm matrix was confirmed by the example of St. Aureus . It was found that pillar[5]arene at a concentration of 10 -5 M was able to reduce the thickness of the St. Aureus biofilm by 15%.

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.

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. Using UV-vis, 2D 1H-1H NOESY, and DOSY NMR spectroscopy, the pillar[5]arene was shown to form complexes with the antimicrobial drug moxifloxacin in a 2:1 composition (logK11 = 2.14 and logK12 = 6.20). Films containing moxifloxacin effectively reduced Staphylococcus aureus and Klebsiella pneumoniae biofilms formation on adhesive surfaces.

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. The formation of stable spherical nanosized macrocycle/binase complexes with an average particle size of 200 nm was established by dynamic light scattering and transmission electron microscopy. Flow cytometry demonstrated the ability of macrocycle/binase complexes to penetrate into tumor cells where they exhibited significant cytotoxicity towards A549 cells at 10 -5 -10 -6 M while maintaining the enzymatic activity of binase., (Copyright © 2021 Elsevier Inc. All rights reserved.)

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. The resulting systems can be used as universal drug delivery systems. It was shown by turbidimetry that the obtained pillar[5]arene/synthetic meroterpenoid systems do not interact with the model cell membrane at pH = 7.4, but the associates are destroyed at pH = 4.1. In this case, the synthetic meroterpenoid is incorporated into the lipid bilayer of the model membrane. The characteristics of supramolecular self-assembly, association constants and stoichiometry of the most stable pillar[5]arene/synthetic meroterpenoid complexes were established by UV-vis spectroscopy and dynamic light scattering (DLS). It was shown that supramolecular amphiphiles based on pillar[5]arene/synthetic meroterpenoid systems form monodisperse associates in a wide range of concentrations. The inclusion of the antitumor drug 5-fluoro-2'-deoxyuridine (floxuridine) into the structure of the supramolecular associate was demonstrated by DLS, 19F, 2D DOSY NMR spectroscopy.

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. According to the fluorescence spectroscopy data, a dramatic fluorescence enhancement in the pillar[5]arene/fluorescein/polymer system was observed with decreasing pH from neutral (pH = 7) to acidic (pH = 5). This indicates the destruction of associates and the release of the dye at a pH close to 5. The presented results open a broad range of opportunities for the development of new universal stimulus-sensitive drug delivery systems containing macrocycles and nontoxic tetrazole-based polymers.

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 p -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). The powders are able to selectively adsorb up to 46% of nitrophenols from water and were incorporated into an electrochemical sensor to selectively recognize them in aqueous acidic solution.

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 + (CH 3 ) 2 R, R = CH 2 Ph, C n H 2n+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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Synthetic organic 2D materials are attracting careful attention of researchers due to their excellent functionality in various applications, including storage batteries, catalysis, thermoelectricity, advanced electronics, superconductors, optoelectronics, etc. In this work, thiacalix[4]arene derivatives functionalized by geranyl fragments at the lower rim in cone and 1,3-alternate conformations, that are capable of controlled self-assembly in a 2D nanostructures were synthesized. X-ray diffraction analysis showed the formation of 2D monomolecular-layer nanosheets from synthesized thiacalix[4]arenes, the distance between which depends on the stereoisomer used. It was established by DSC, FSC, and PXRD methods that the obtained macrocycles are capable of forming different crystalline polymorphs, moreover dimethyl sulphoxide (DMSO) is contributing to the formation of a more stable polymorph for cone stereoisomer. The obtained crystalline 2D materials based on synthesized thiacalix[4]arenes can find application in material science and medicine for the development of modern pharmaceuticals and new generation materials.

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. This review discusses the successes in the synthesis and practical application of both natural and synthetic macrocycles. Among the natural macrocyclic meroterpenoids, special attention is paid to isoprenylated flavonoids and phenols, isoprenoid lipids, prenylated amino acids and alkaloids, and isoprenylpolyketides. Among the synthetic macrocyclic meroterpenoids obtained by combining the "classical" macrocyclic platforms, those based on cyclodextrins, together with meta- and paracyclophanes incorporating terpenoid fragments, and meroterpenoids obtained by macrocyclization of several terpene derivatives are considered. In addition, issues related to biomedical activity, processes of self-association and aggregation, and the formation of host-guest complexes of various classes of macrocyclic merotenoids are discussed in detail.

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. Although many examples exist where calixarenes encapsulate, or incorporate, antimicrobial drugs, one of the main factors to emerge is the ability of functionalized macrocycles to engage in multivalent interactions with proteins, and thus inhibit cellular aggregation.

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). Using DLS and SEM it was found that upon concentration and/or evaporation of the solvent, the supramolecular polymer (pillar[5]arene/vitamin D3 (1 : 2)) forms a porous material with an average wall diameter of 53 nm. It was shown that the supramolecular polymer is stable during photolysis by UV radiation (k1 = 1.7 × 10-5 s-1).

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. In this paper, we reported a straightforward approach to the synthesis of interpolyelectrolytes by co-assembling of the thiacalix[4]arene with four negatively charged functional groups on the one side of macrocycle, and pillar[5]arene with 10 ammonium groups located on both sides. Nanostructured polyelectrolyte complexes show effective packaging of high-molecular DNA from calf thymus. The interaction of co-interpolyelectrolytes with the DNA is completely different from the interaction of the pillar[5]arene with the DNA. Two different complexes with DNA, i.e., micelleplex- and polyplex-type, were formed. The DNA in both cases preserved its secondary structure in native B form without distorting helicity. The presented approach provides important advantage for the design of effective biomolecular gene delivery systems.

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. The results can be used to create new antibacterial materials and 2D biomedical coatings., (Copyright © 2020, Shurpik et al.; licensee Beilstein-Institut.)

Novel ammonium and betaine derivatives of p-tert-butylthiacalix[4]arene in cone and 1,3-alternate conformation were synthesized with high yields for the first time. The obtained compounds form in water spherical nanoparticles. It was shown by molecular docking calculations and in vitro experiments that amino and betaine derivatives can inhibit acetylcholinesterase and butyrylcholinesterase on the level of pyridostigmine while the toxicity of the obtained compounds is much lower than that of pyridostigmine., (Copyright © 2019 Elsevier Inc. All rights reserved.)

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. The structure of the inclusion complex of the pillar[5]arene with rocuronium bromide was additionally investigated by quantum chemical methods.

Products of lactic acid polycondensation (poly- and oligolactic acids) are widely used as packaging materials, drug delivery agents, implants etc. Variety of their applications is caused by a number of practically important properties, e.g., biocompatibility and biodegradability, non-toxicity, and mechanical durability. Modification of these polymers with different additives allows improving their properties and extending future applications. In this manner, stability toward degradation, recognition of some substrates, extended thermal stability etc. can be improved. Macrocyclic compounds are promising candidates as modifiers. They are able to provide polymer materials with additional binding sites, impart certain orientation to spatial arrangement of polymer chains, change hydrophilic-lipophilic balance, and redox properties. The latter one can be used for assembling various electrochemical sensors and biosensors that combine steric discrimination of the analytes caused by oligolactides and highly sensitive response to their quantities caused by redox labels introduced. Different composite materials based on oligolactides as matrices for such redox labels were described in the assemblies of biosensors for drugs, pesticides, and antioxidants detection. In this mini-review, methods for the synthesis of the lactic acid oligomers and those modified with the macrocyclic fragments (porphyrin, cyclodextrin, and cyclophane) have been described. The effects of modifiers on complexation, thermal, and aggregation properties of materials are described. Analytical performance of oligolactide based sensors and biosensors has been considered with particular emphasis to the mechanism of signal generation.

Synthesis and application of nanostructured materials applicable in the assembly of electrochemical sensors is one of the important trends in material sciences and analytical chemistry. In this work, we have proposed and implemented simple non-template method for assembling nanofibers from the polyaniline ultrasonicated with phenyliminophenothiazine in aqueous media. Two-step procedure including association with emeraldine dispersion and reorganization under ultrasonication led to formation of nanofibrillar structures with average diameter of 20 nm. UV-spectroscopy confirms that association of phenyliminophenothiazine and polyaniline in acidic medium resulted in an intense absorption band at 900-910 nm due to donor-acceptor interaction between the reactants. The material combined emeraldine charge transmission with redox activity of phenyliminophenothiazine was found promising for electrochemical sensing. It was confirmed by comparison of characteristics of appropriate solid-contact sensors based on emeraldine and phenyliminophenothiazine toward Fe(III) ions, ascorbic acid and hydroquinone. In all the cases, the use of phenyliminophenothiazine results in a wider concentration range and more reproducible signal against characteristics of similar sensor based on polyaniline. The applicability of the sensor was confirmed by determination of iron content in commercial medication.

New solid-contact potentiometric sensors have been developed for hydrogen phosphate recognition on the basis of ionic liquids containing tetrasubstituted derivatives of thiacalix[4]arene in cone and 1,3-alternate conformations with trimethyl- and triethylammonium fragments at the lower rim substituents. The recognition of selected anions including carbonate, hydrogen phosphate, perchlorate, oxalate, picrate, and EDTA was conducted using electrochemical impedance spectroscopy with ferricyanide redox probe. For the potentiometric sensor assembling, the ionic liquids were stabilized by multiwalled carbon nanotubes and carbon black deposited on the glassy carbon electrode. The influence of support, steric factors and modification conditions on the sensor performance has been investigated. As was shown, potentiometric sensors developed make it possible to selectively determine hydrogen phosphate anion within the concentration range from 1 × 10 -2 to 1 × 10 -6 M and limit of detection of 2 × 10 -7 -1 × 10 -6 M with unbiased selectivity coefficients varied from 1.2 × 10 -1 to 1.0 × 10 -8 (carbonate, acetate, oxalate, succinate, glutharate, glycolate, and malonate anions).

New p - tert -butylthiacalix[4]arenes, which are mono-, 1,2-di- and tetrasubstituted at the lower rim containing N -(4'-nitrophenyl)acetamide and N , N -diethylacetamide groups in cone and partial cone conformations have been synthesized. Their complexation ability towards a number of tetrabutylammonium salts n -Bu 4 NX (X = F - , Cl - , Br - , I - , CH 3 CO 2 - , H 2 PO 4 - , NO 3 - ) was studied by UV spectroscopy. The effective receptor for the anions studied as well as selective receptors for F - , CH 3 CO 2 - and H 2 PO 4 - ions, which based on the synthesized thiacalix[4]arenes, have been obtained. It was shown that p - tert -butylthiacalix[4]arene tetrasubstituted at the lower rim by N -(4'-nitrophenyl)acetamide moieties bonded to the anions studied with association constants within the range of 3.55 × 10 3 -7.94 × 10 5 M -1 . Besides, the binding selectivity for F - , Cl - , CH 3 CO 2 - , and H 2 PO 4 - anions against other anions was in the range of 4.1-223.9. Substituting one or two fragments in the macrocycle with N , N -diethylacetamide groups significantly reduces the complexation ability of the receptor. In contrast to the 1,3-disubstituted macrocycle containing two N -(4'-nitrophenyl)acetamide moieties, the 1,2-disubstituted thiacalix[4]arene, which contains only one such fragment and a N , N -diethylacetamide moiety, selectively binds F - anions.

New water-soluble tetra-substituted derivatives of p-tert -butylthiacalix[4]arene containing fragments of L-tryptophan in cone and 1,3- alternate conformations were obtained. It was shown that the resulting compounds form stable, positively charged aggregates of 86-134 nm in diameter in water at a concentration of 1 × 10 -4 M as confirmed by dynamic light scattering, scanning electron microscopy and transmission electron microscopy. It was established that these aggregates are fluorescently active and chiral. A distinctive feature of the compounds is the pronounced dependence of their spectral (emission and chiroptical) properties on the polarity of the solvent and the length of the linker between the macrocyclic and fluorophore parts of the molecule.

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.

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.

New acetylcholinesterase (AChE) biosensor based on unsubstituted pillar[5]arene (P[5]A) as electron mediator was developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. The AChE from electric eel was immobilized by carbodiimide binding on carbon black (CB) placed on glassy carbon electrode. The working potential of 200mV was obtained in chronoamperometric mode with the measurement time of 180 s providing best inter-biosensors precision of the results. The AChE biosensor developed made it possible to detect 1×10(-11)-1×10(-6) M of malaoxon, 1×10(-8)-7×10(-6) M of methyl-paraoxon, 1×10(-10)-2×10(-6) M of carbofuran and 7×10(-9)-1×10(-5) M of aldicarb with 10 min incubation. The limits of detection were 4×10(-12), 5×10(-9), 2×10(-11) and 6×10(-10) M, respectively. The AChE biosensor was tested in the analysis of pesticide residuals in spiked samples of peanut and beetroot. The protecting effect of P[5]A derivative bearing quaternary ammonia groups on malaoxon inhibition was shown., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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.

New water-soluble p-tert-butylthiacalix[4]arenes containing peptide and quaternary ammonium fragments in cone and 1,3-alternate conformations were synthesized and characterized. The interaction of the macrocycles with DNA was studied by UV-spectroscopy, DLS and TEM. It was shown that the interaction of the self-associates based on p-tert-butylthiacalix[4]arenes tetrasubstituted at the lower rim with glycine and quaternary ammonium fragments in cone and 1,3-alternate conformations with DNA led to the formation of particles of about 99-192 nm in size.

New acetylcholinesterase (AChE) sensor based on Ag nanoparticles decorated with macrocyclic ligand has been developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. AChE was immobilized by carbodiimide binding on carbon black (CB) layer deposited on a glassy carbon electrode. The addition of Ag nanoparticles decreased the working potential of the biosensor from 350 to 50 mV. The AChE sensor made it possible to detect 0.4 nM-0.2 μM of malaoxon, 0.2 nM-0.2 μM of paraoxon, 0.2 nM-2.0 μM of carbofuran and 10 nM-0.20 μM of aldicarb (limits of detection 0.1, 0.05, 0.1 and 10 nM, respectively) with 10 min incubation. The AChE sensor was tested for the detection of residual amounts of pesticides in spiked samples of peanut and grape juice. The protecting effect of new macrocyclic compounds bearing quaternary ammonia fragments was shown on the example of malaoxon inhibition., (Copyright © 2014 Elsevier B.V. All rights reserved.)

New aptasensors based on DNA aptamer and polycarboxylated thiacalix[4]arenes in cone, 1,3-alternate and partial cone configurations bearing Neutral Red (NR) at substituents at the lower rim have been developed and applied for thrombin detection. The assembly of the biorecognition layer was optimized by AFM and EIS study to reach the maximal coverage and regular composition of the surface layer. The interaction of the NR groups with thrombin suppressed the electron hopping between oxidized and reduced mediator groups. This regularly decreased the NR peak current and increased the resistance of the charge transfer. The aptasensor makes it possible to detect from 1 nM to 1 μM of thrombin with the detection limit of 0.05-0.5 nM. No effect of the 1000 excess of bovine serum albumin on the signal was observed. The influence of thiacalix[4]arene configuration on the sensitivity of aptasensor signal toward thrombin is discussed., (Copyright © 2012 Elsevier B.V. All rights reserved.)

In this work, the formation of two- and three-component supramolecular systems based on cone, partial cone, 1,3-alternate stereoisomers of heteroditopic "hosts": p-tert-butylthiacalix[4]arene containing 4-amidopyridine fragments with silver(I) cations and dicarboxylic acids in liquid and solid phases were studied by UV spectroscopy, dynamic light scattering, and atomic force microscopy methods. It has been shown that these macrocycles are coreceptors, capable of simultaneously binding silver(I) cations, dicarboxylic acids (oxalic, malonic, succinic, maleic, fumaric acids), and hydroxyl acids (glycol, tartaric acids). For the first time, by the dynamic light scattering method, it has been shown that the conformation of p-tert-butyl thiacalix[4]arenes significantly affects the type of three-component system formed: cone is characterized by the formation of cascade systems; for partial cone, intermediate systems; and for the 1,3-alternate stereoisomers, three types of three-component systems (cascade, intermediate, and commutative) were observed., (© 2011 American Chemical Society)

New p-tert-butyl thiacalix[4]arenes differently substituted at the lower rim with amide, hydroxyl and ester groups were synthesized. Binding properties of the compounds toward some tetrabutylammonium salts n-Bu(4)NX (X = F(-), Cl(-), Br(-), I(-), CH(3)CO(2)(-), H(2)PO(4)(-), NO(3)(-)) were studied by UV spectroscopy. It was found that the stoichiometry of the complexes, generally, is 1 : 1, and the association constants are in the range of 10(3)-10(5) M(-1). The p-tert-butyl thiacalix[4]arenes containing secondary amide groups trisubstituted at the lower rim bind the studied anions most effectively. Selective receptors for fluoride and dihydrogen phosphate salts of tetrabutylammonium were found.

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., (Copyright 2010 Elsevier B.V. All rights reserved.)

The ability of p-tert-butyl thiacalix[4]arenes functionalized with tertiary and secondary amide and hydrazide groups at the lower rim in cone, partial cone, and 1,3-alternate conformations to self-assemble and recognize metal ions of s- (Li(+), Na(+), K(+), Cs(+)), p- (Al(3+), Pb(2+)) and d- (Fe(3+), Co(3+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Hg(2+)) elements was investigated by picrate extraction method and dynamic light scattering (DLS). DLS was used for determination of the hydrodynamic diameter, polydispersity index, and molecular weight of nanoscale aggregate systems consisting of p-tert-butyl thiacalix[4]arene molecules and metal nitrates. Also for quantitative determination of the dimer shape from the values of molecular weight and the particles size, the Perrin factor (F) was established. It was shown that in most cases the dimers of stereoisomers of p-tert-butyl thiacalix[4]arenes tetra-substituted at the lower rim by secondary amide groups represent the prolate spheroid.

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.

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).