The contemporary state of the art has been considered in the field of colloidal solutions of complexes of synthetic and natural polyelectrolytes with some supramolecular macrocycles (calix[n]arenes, calix[4]resorcinols, pillar[n]arenes, and calix[4]pyridinium) bearing charged groups. Examples of the obtained polymer complexes have been presented, and their characteristics (sizes and electrokinetic potentials) and properties (sensitivity to stimuli, capability of encapsulation, and cytotoxicity), as well as the potential of their application, have been described.

The synthesis of colloidal platinum nanoparticles (PtNPs) (d(core) approximate to 1-40 nm) in an aqueous solution was carried out using amido(dimethyl)amino- and carboxy- calix[4]resorcinarenes with alkyl substituents on the lower rim as stabilizer. The nanoparticles were characterized by spectrophotometry, IR, TEM, DLS, PXRD and SAXS. It was shown that PtNPs and gold nanoparticles (AuNPs) obtained, stabilized by calix[4]resorcinarenes, demonstrate the photocatalytic activity in the photodegradation of methyl orange and rhodamine B toxic dyes under visible light irradiation. The rate constants of catalytic reaction (K-1, min(-1)) and activity of nanocatalysts (K-2, min(-1) mol(-1)) were calculated. It was found that size of metal core, structure of macrocycle stabilizing the surface of metal nanoparticles, its ability to form self-associates and bind dye molecules define the rate of dye photodegradation reaction. The study of the interaction of PtNPs and AuNPs capped with amidoamine macrocycles with organic photolinkers by spectrophotometry and fluorescence showed the binding of photolinkers by macrocycles, PtNPs and AuNPs. The photocatalytic activity of obtained cooperative nanoassociates was studied. The addition of photolinkers leads to both an increase and a decrease in the reaction rate, depending on the structure of linker and macrocycle. An increase in the reaction rate occurs due to the formation of photoactive supramolecular nanoassociates and the additional photosensitizing action of the photolinker on the surface of a metal nanoparticle. Such hybrid nanocatalysts based on metal nanoparticle and calixresorcinarenes have the potential to be used in the field of effective photodegradation of toxic water pollutants.

The data provided in this paper are associated with the data in the «Binding of L-tryptophan and bovine serum albumin by novel gold nanoparticles capped with amphiphilic sulfonatomethylated calixresorcinarenes» paper (Shalaeva et al., 2019). Here, we represent i) the characterization data of calixresorcinarenes capped gold nanoparticles obtained by TEM and Vis- and IR spectroscopy; ii) the data giving the information about the interaction of modified AuNPs with L-tryptophan and bovine serum albumin by dynamic light scattering, spectrophotometry and fluorescence spectroscopy.

Small (dcore ≈ 2–5 nm) well-dispersed gold nanoparticles (AuNPs) stabilized by amphiphilic octacarboxy-calix[4]resorcinarenes with different substituents on the lower rim—methyl (С1–CR), pentyl (С5–CR) and undecyl (С11–CR)—in an aqueous solution were obtained. The nanoparticles were studied by spectrophotometry, transmission electron microscopy, FTIR-spectroscopy, dynamic light scattering, small angle X-ray scattering and X-ray powder diffraction. The influence of HAuCl4/macrocycle ratio during the synthesis on the nanoparticles size and aggregation only for weakly associated С1–CR and С5–CR was achieved. The self-association effect of С11–CR on the nanoparticles stabilization is found. The existence of gold in the form of crystallites and their average sizes were defined. The average nanoparticle sizes were determined and the structure of macrocyclic shells on the surface of nanoparticles in an aqueous solution was proposed. The formation of cooperative calix[4]resorcinarene associates on the AuNPs surface due to the multiple supramolecular interactions leads to the creation of functional gold nanoparticles.

The association of branched polyethyleneimine (PEI) with a series of octacarboxy-calixresorcinarenes bearing different low-rim substituents leads to the formation of nanosized supramolecular complexes. The PEI-macrocycle complexes have fine-tunable sizes regulated by variations in the self-association capacity of the calixresorcinarenes. In the supramolecular complexes, hydrophobic fragments of the polymer and calixresorcinarenes form cooperative hydrophobic domains which provide synergistic enhancement of guest molecule binding. The formation of the supramolecular complexes was investigated by NMR FT-PGSE, NMR 2D NOESY, DLS and TEM methods. In addition, fluorimetry and UV-vis methods were used with the help of optical probes, namely water-soluble Crystal Violet and water-insoluble Orange OT. The investigation demonstrates the first example of the formation of cooperative hydrophobic domains in supramolecular polyelectrolyte-macrocycle complexes which enhance the binding of both water-soluble and water-insoluble organic compounds. The presented supramolecular systems have potential as sensory and drug delivery systems.

Cooperative nanoscale associates of amido(dimethylamino) calixresorcinarenes with pentyl (C5) and undecyl (C11) substituents on lower rim with antitumor drug-methotrexate (MTX) in aqueous solution and on the surface of gold nanoparticles C5@Au and C11@Au were formed. The formation of nanoparticles was investigated by H-1 NMR, NMR FT-PGSE, 2D NOESY, DLS, TEM, spectrophotometry, fluorimetry. It was found that during the interaction of C5 or C11 macrocycles with MTX in aqueous solution, the latter generates dissociation of macrocycles self-associates with formation of cooperative macrocycle-MTX associates of smaller size due to multiple non-covalent interactions, which leads to increase in fluorescence intensity of MTX. In contrast, binding of MTX by macrocyclic associates preorganized as bilayer on surface of gold nanoparticles through electrostatic interactions induces aggregation of C5@Au-MTX or C11@Au-MTX associates, which results in quenching of MTX fluorescence in solution. Such particles have possible potential in the field of binding and delivery of antitumor drugs.[GRAPHICS].

The water-soluble tetramethylensulfonatocalix[4]resorcinarene with methyl (C1) and pentyl (C5) substitutes on the lower rim forms colloid nanoscale aggregates with poly(diallyldimethylammonium chloride) (PDDA) in aqueous solutions. The size and stability of nanoparticles depend on concentrations of the components and their ratio in the calixarene-polymer' system. Ternary supramolecular complexes << polymer-macrocycle-guest molecule L-tryptophan (Trp) in conditions of spontaneous pH (3.80 and 4.78 for C1-PDDA and C5-PDDA systems, respectively) in an aqueous solution and in phosphate buffer (pH 7) were investigated by fluorescence method. The addition of the third component - PDDA - to the << non-aggregated C1-Trp >> associates leads to the release of Trp in all studied conditions. The possibility of the << binding-release >> process of L-tryptophan in << C5-Trp >> associates after PDDA addition in the ternary complex is achieved and controlled by the structure of the macrocyclic self-associates and pH conditions.[GRAPHICS].

Novel water-soluble thermoresponsive oligomers TO1 and TO2 were obtained by reaction of amidoamine tetramethylcalixresorcinarenes (C1) and tetrapentylcalixresorcinarenes (C5) with ethylene glycol diglycidyl ether. The compounds were characterised by H-1 and FT-PGSE NMR, FTIR, static light scattering and elemental analysis. The thermoresponsive properties of oligomers were investigated by spectrophotometry, DLS, FT-PGSE NMR and TEM. The cloud points of oligomers (43 degrees C for TO1 (5mg/ml) and 41 degrees C for TO2 (1.2mg/ml), respectively) were determined. The influence of salts effect on TO2 cloud points was investigated. The binding of anti-inflammatory drug naproxen (Nap) at 20 degrees C by TO1 and TO2 and its partial release at cloud points of oligomers in aqueous solution are observed using fluorescence and FT-PGSE NMR methods. New example of creating of thermoresponsive macrocyclic systems on the basis of amidoamine calixresorcinarenes with possibility of substrate binding and release under the influence of termo-stimuli in an aqueous solution was shown.

Amido(dimethylamino) calix[4]resorcinarenes with different substituents on the lower rim (-CH3 (C1), -C5H11 (C5), -C11H23 (C11)) both as reducing and stabilizing agent in an aqueous solution were used for the fabrication of stable gold colloids. Gold colloids are characterized by spectrophotometry, FTIR - spectroscopy, transmission electron microscopy, dynamic light scattering. It is found that increase of the macrocycle's concentration towards HAuCl4 concentration during the synthesis leads to the decrease in the size of formed particles. It is shown that the size of gold nanoparticles (AuNPs) decreases with the increase of the hydrophobicity of the substituents on the macrocycles lower rim (C1@Au - 4-14 nm, C5@Au - 10-11 nm, C11@Au - 7-8 nm). The monolayer packing of the macrocycle molecules on the surface of the metal particle for C1@Au and bilayer - for C5@Au and C11@Au, providing both the stabilization of AuNPs and their solubility in water, are proposed. Temperature and pH variation during the synthesis showed that the optimal synthesis conditions for all kinds of particles C1@Au, C5@Au, C11@Au are spontaneous installed during the synthesis pH (for C1@Au - pH 8.10, C5@Au - pH 8.56, C11@Au - pH 8.63) and the synthesis temperature of the 25 degrees C.High binding fraction of drug substrate naproxen on the surface of AuNPs modified by C5 and C11 macrocyclic aggregates due to the ordering of the macrocycles on the particle surface and enhancing their receptor ability towards naproxen is defined by fluorescence method.

The association of cetylpyridinium chloride (CPC) micelles in the presence of octaacetated tetraphenyleneoxymethylcalix[4]resorcinarene (CR) leads to the formation of unusual spherical supramolecular nanoparticles (SNPs). Within the range of CR/CPC molar ratios from 10/1 to 1/10 (except for 1/8), CR, acting as a counterion, decreases the critical micelle concentration of CPC by one order of magnitude and leads to the formation of SNPs with an average hydrodynamic radius of 164 nm and an average zeta potential of -60 mV. The formation of SNPs was studied by NMR FT-PGSE and 2D NOESY, DLS, TEM, fluorimetry, and UV-Vis methods. The stability of SNPs at different temperatures and pH values and in the presence of electrolytes was investigated. The specificity of the interactions of the SNPs with substrates that were preferentially bound by a macrocycle or CPC micelle was studied. The enhancement of cation dye binding in the presence of SNPs is shown. The presented supramolecular system may serve as a nanocapsule for water-soluble and water-insoluble compounds.

Here we represent the first example of the formation of mixed nanoscale associates, constructed from amphiphilic calixresorcinarenes and hydrophobic carboxylic acids including drugs. The amidoamino-calixresorcinarene self-associates effectively solubilize hydrophobic carboxylic acids - drugs such as naproxen, ibuprofen, ursodeoxycholic acid and aliphatic dodecanoic acid - with the formation of the mixed aggregates with the macrocycle/substrate stoichiometry from 1/1 to 1/7. The ionization of organic acids and the peripheral nitrogen atoms of the macrocycles with the subsequent inclusion of hydrophobic acids into the macrocycle self-associates is the driving force of solubilization. In some cases, this leads to the co-assembly of the macrocycle polydisperse associates into supramolecular monodisperse nanoparticles with the diameter of about 100 nm. The efficiency of drug loading into the nanoparticles is up to 45% and depends on the structure of organic acid. The dissociation of the mixed aggregates and release of organic acid are attained by decreasing pH.

In the solutions of polyacrylic acid (PAA) the amphiphilic calix[4]resorcinarenes 1-10 and their complexes with Methyl Orange (MO) form binary (1-10)-PAA and tertiary (2-10)-MO-PAA supramolecular complexes which are water-soluble in the case of amidoammonium (1-5) and water-insoluble in the case of amidoamino (6, 7) or amido(dimethylamino) (8-10) calixresorcinarenes. Almost 90% of removal of MO from the aqueous solution is achieved by the formation of the water-insoluble systems (6-10)-MO-PAA. In aqueous solution the particles of the (1-5)-PAA systems have average hydrodynamic diameters which values vary depending on the length of the alkyl substituents of macrocycles. (C) 2015 Elsevier B.V. All rights reserved.