At present, multifunctional adsorbents capable of not only effectively binding metal ions but also maintaining stability under aggressive conditions (e.g., in an acidic medium) are of great interest. In this work, Cu(II) and Co(II) complexes based on hyperbranched polyester polyphthalate are obtained and characterized for the first time. Complexation is confirmed by IR and electron spectroscopy methods, which revealed the monodentate nature of the coordination of carboxylate groups and the formation of covalent bonds with metals. The coordination units of the complexes have a six-coordinated octahedral geometry with tetragonal distortion, and the ligand:metal molar ratio is 4:1. Calculation of the stability constants showed high stability of the complexes with logarithms of the constants of 18.11 for Cu(II) and 17.23 for Co(II). The TGA method established that the onset temperature of destruction of the copper and cobalt complexes is 210 and 252°C. The ligand demonstrated high sorption capacity for Cu(II) and Co(II) ions—47.88 and 28.21 g/kg, respectively, while desorption was not observed even at low pH (1), which indicates the strength of the complex bonds. These results indicate the possibility of using the macroligand as a sorbent in an acidic environment, for example, in the purification of industrial wastewater and mine waters.

Metal complexes of hyperbranched polymers have attracted attention as potential catalysts due to their unique, tunable structure. Hyperbranched polyester polybenzoylcarbamate was synthesized by the reaction of second-generation hyperbranched polyester polyol with benzoyl isocyanate. The structure was studied by 1H, 13C NMR, and IR spectroscopies. The degree of functionalization as determined by 1H NMR spectroscopy was 25

A first-generation aminoethylene carbonate dendrimer was synthesized by the polycondensation reaction of triethanolamine with dimethyl carbonate in bulk. The dendritic architecture of the oligomer was confirmed by 1H, 13C NMR, IR and UV spectroscopy, titrimetry, viscometry and elemental analysis. The dendrimer has 6 terminal hydroxyl groups, the degree of branching is 1, and the number-average and viscosity-average molecular weights are 674 and 871 g∙mol-1, respectively. The thermal transformations were investigated by TGA and DTA methods. The spherical morphology of oligoaminoethylene carbonate was confirmed by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). The hydrodynamic particle diameter and polydispersity of the agglomerates of oligomer were established by nanoparticle trajectory analysis (NTA) and dynamic light scattering methods. The phase state of the oligomer was established by RSA method. The kinematic viscosity, refractive index and solubility in organic solvents and water were determined. The aminoethylene carbonate dendrimer can serve as a platform for targeted drug delivery and is of interest as a ligand for complexes with transition metals and catalytic systems.

A second-generation hyperbranched polyester with the terminal carbamoyl phosphonate groups has been synthesized. The structure of the resulting polyester has been studied by IR, 1H NMR, 31P NMR, and electron spectroscopy. It has been found that 25

Hyperbranched polymers are densely packed macromolecules whose three-dimensional framework consists of a core and three or more branched short composite chains, namely dendrons. They have a spherical architecture and unique properties, such as nanoscale macromolecules (2–100 nm), high solubility, the presence of several branched chains, spatial voids and a large number of end functional groups. Various classes of hyperbranched polymers in the last 10 years such as polyalkanes, polyarylenes, polyhalides, organometallic polymers, polyethers, polyesters, nitrogen-containing and polyheterocyclic compounds are reviewed. These polymers can be readily obtained under mild conditions by polymerization, polycondensation or polycoupling reactions of polyfunctional monomers. The main characteristics confirming the hyperbranched structure of polymers are: low molecular weight, dispersity, medium degree of branching, large number of end functional groups, nanoscale macromolecules, three-dimensional architecture, presence of glass transition temperature, high solubility in various organic solvents, and low viscosity of polymer solutions. Due to their adaptable structures and special properties, hyperbranched polymers are widely used as hybrid materials and composites for structural applications, coatings, adhesives, membranes, catalysts, flame retardants, plasticizers, and light-emitting materials. The hyperbranched structure combined with low toxicity allows their use as highly effective nanoscale anticancer and bactericidal drugs, as well as contrast reagents for magnetic resonance tomography. The availability of technologically significant methods for the synthesis of hyperbranched polymers of various types makes it possible to carry out their industrial production on a scale sufficient for practical application in solving modern problems of biomedical chemistry and in many other branches of science and industry.

A new complex 3 of aminoethylene carbonate dendrimer with Pd(II) ions was synthesized on an ɣ-aluminum oxide support in three stages. At the first stage, γ-aluminum oxide with surface methyl carbonate groups was obtained by reaction of γ-aluminum oxide with dimethyl carbonate. At the second stage, hybrid composite 2 was synthesized by reaction of modified γ-aluminum oxide 1 with aminoethylene carbonate dendrimer. At the third stage, complex 3 was obtained by reaction of hybrid composite 2 with palladium(II) chloride. Using infrared (IR) spectroscopy, X-ray diffraction analysis (XRD), confocal laser scanning (CLSM) and optical microscopy, the structure and spherical morphology of particles of modified γ-aluminum oxide 1, hybrid ligand 2 and complex 3 were confirmed. Pd(II) ions in complex 3 was reduced to Pd(0) 4 nanoparticles in toluene at a temperature of 53°C and a pressure of 0,11 MPa for 3 hours in a hydrogen flow. Next, the resulting nanosized composite material 4 was used as a catalyst for the reaction of selective hydrogenation of α-methylstyrene to cumene. Palladium catalyst 4 showed high catalytic activity under mild conditions with an activation energy Ea = 43,6 kJ mol-1. Using IR spectroscopy and microscopy, it was established that the structure and spherical morphology of catalyst 4 is preserved even after the hydrogenation of α-methylstyrene. The results obtained indicate the promise of using a new metal-polymer hybrid material as a catalyst for the hydrogenation of unsaturated compounds.

The PdII complex was synthesized on the platform of hyperbranched polyester polyphthalate. The polymeric ligand and complex were characterized by different methods, including 1H NMR, IR spectroscopy, electron spectroscopy in the visible and UV ranges, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), electron microscopy, nitrogen adsorption/desorption, temperature-programmed reduction (TPR) in a hydrogen flow, and XRD. The polymer macromolecule was found to contain ten terminal phthalate groups. The PdII complex is characterized by the ratio ligand: PdII = 2: 5 and contains a square-planar coordination site, which favors the formation of a cluster with the predominant pore diameter from 2 to 10 nm. After the reduction of the PdII complex in a hydrogen flow, Pd0 nanoparticles stabilized on the polymer substrate were obtained. The complex showed a high catalytic activity in the reduction of α-methylstyrene to cumene under mild conditions.

Hyperbranched polymers are successful nanoscale functional platforms for loading metal ions and creating promising nanomaterials for medicine. This work presents the synthesis of metal-polymer nanostructures based on a second generation hyperbranched polyester with eight terminal benzoylthiocarbamate (BTC) groups loaded with Gd(III) or Dy(III) ions. Their structure (Fourier transform infrared spectroscopy) and morphology (transmission electron microscopy), photophysical (ultraviolet-visible and luminescence spectroscopy), thermophysical, magnetic activity, relaxivity, and aggregation properties (nanoparticle tracking analysis) were studied. The formation of the metal-polymer complex is carried out by chelation of lanthanide ions -C & boxH;O and -C & boxH;S groups of the BTC fragment of polyester. Coordination units with composition Ln(III)-3BTC (Ln = Dy, Gd) were localized on the branched polymer platform. The load is three lanthanide ions per branched polyester polybenzoylthiocarbamate macromolecule. Logarithms of stability constants of complexes and composition of coordination polyhedron have been determined. The dysprosium complex is in a paramagnetic state with antiferromagnetic correlations, and the gadolinium complex is in a paramagnetic state. The relaxivity of the Dy(III) and Gd(III) complexes increased by 2.5 and 3 times, respectively, compared to their nitrates. An important achievement is the identification of rare-earth metal (REM)-controlled morphology and self-organization for Dy(III) and Gd(III) complexes with branched polyester polybenzoylthiocarbamate in solution and on the surface. Spherical nanostructures for the dysprosium complex and nanorods for the gadolinium complex were observed. Synthesized REM-loaded nanostructures with polyester polybenzoylthiocarbamates have low hemotoxicity and can be applied in biomedicine.

The hare skin has weak leather tissue, which requires filling and tanning in order to prolong the period of use of products. To strengthen hare skin it was proposed to use aminoethylene carbonate dendrimer, which was first synthesized by the reaction of triethanolamine with dimethyl carbonate. The dendrimer was characterized by 1H NMR and IR spectroscopy, elemental analysis, TGA, SEM and dynamic light scattering. The aminoethylene carbonate molecule contains 6 terminal hydroxyl groups and has a number-average molecular weight of 674 g∙mol-1. The hare skins treated with chrome tanning agent, with and without dendrimer, have close shrinkage temperatures. However, the experimental samples filled with dendrimer show better physical and mechanical properties, higher degree of thickening and ordered dermis structure compared to the control samples. This study shows the effectiveness of using aminoethylene carbonate dendrimer as a retanning agent for hare skin.

Polymer metal-organic framework (MOF) are a new class of hybrid porous materials that combine the ad-vantages of both organic polymers and metal-organic frameworks. In this regard, a new ligand was synthesized - a hyperbranched polyester polybenzoylthiocarbamate, the structure of which was established by IR, H-1 NMR, electron spectroscopy and elemental analysis. Complexing properties have been studied using the example of Cu(II) and Co(II) ions. The formation of metal-polymer clusters with metal ions with the participation of benzoylthiocarbamate groups of the polyester has been proved by IR, electron spectroscopy and electron microscopy. It was found that the structure of coordination sites is octahedral with tetragonal distortions. The compositions and conditional logarithms of the stability constants of the complexes were determined. (c) 2022 Elsevier B.V. All rights reserved.

For the first time, metal–polymer complexes have been synthesized using hyperbranched polyester polyfumaratomaleate as a matrix, the structure of which has been established by 1H NMR, IR, electron spectroscopy, and elemental analysis methods. The formation of complexes with Gd(III) and Dy(III) ions involving fumarate and maleate groups of the polyester was proved by IR and electron spectroscopy methods. It was established that the structure of the coordination units has the form of a square antiprism. The compositions and conditional logarithms of the stability constants of the complexes were determined. It was established that complexation with lanthanide ions promotes emission enhancement in the ligand.

A highly efficient hybrid adsorbent based on an industrially available, biodegradable, non-toxic linencellulose modified with hyperbranched polyesterpolybenzoylthiocarbamate has been synthesized.The synthesis was carried out using as a linkertoluene diisocyanate.The second-generation hyperbranched polyesterpolybenzoylthiocarbamate according to 1H, 13C NMR and IR spectroscopy contains 8 terminal benzoylthiocarbamate and 8 hydroxyl groups.In the first stage, the reaction of toluene diisociant with linen cellulose was carried out. By potentiometric titration, the content of toluene diisociant was found to be 27%. Then, hyperbranched polyesterpolybenzoylthiocarbamate was added to the modified linen cellulose. The content of hyperbranched polymer in cellulose, determined by the weight method, is 5%. Unreacted isocyanate groups are neutralized with isobutyl alcohol. The structure of the hybrid material is proven by IR spectroscopy. The adsorption properties of the polydentate adsorbent were studied with respect to Cu(II) ions. It was found that the adsorption capacity of the adsorbent is 6.93 mg/g. Using DSC and TGA analysis, the temperature characteristics, thermal effects, and mass loss of the obtained polydentate compound and its complexes were determined.It was shown that in an acidic medium at pH 3-4, desorption of Cu (II) and Co (II) ions occurs with the regeneration of a hybrid adsorbent.

The study of self-assembly processes in polymer solutions is the basis of a modern strategy for creating targeting systems for various substrates. In turn, the use of binary polymer/surfactant systems makes it possible to expand the range of polymers for creating drug delivery systems. This article describes the processes of formation of hybrid micelles based on carboxyl-terminal hyperbranched polyester polyol Boltorn H20-[BH20-COOH] and surfactant Triton X-100-[BH20-COOH/TX-100]. Using pH-metry, conductometry, dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and scanning electron microscopy (SEM), it was shown that at pH = 6.5, a monodisperse [BH20-COOH] associate with a hydrodynamic diameter D-h = 79 +/- 10 nm and hybrid micelles [BH20-COOH/TX-100] with D-h = 114.3 +/- 6 nm are formed. Both types of supramolecular associates are able to effectively encapsulate the anticancer drug doxorubicin. The viability analysis of HeLa and MCF-7 cells was performed in the presence of doxorubicin-loaded [BH20-COOH] and hybrid micelles [BH20-COOH/TX-100] in vitro.

Recently, hyperbranched polymers (HBPs), which differ significantly in structure and properties from linear, cross-linked and branched analogs, have become increasingly important. HBP have a spatial unloaded core and a shell of branched monomer units (dendrons), in which functional groups are predominantly located in the surface layer. The size of macromolecules ranges from 2 nm to 100 nm. Currently, there are a fairly large number of publications in the literature devoted to the modification of hyperbranched polyester polyols with various functional groups and the assessment of the potential for their use. However, there are no review articles on this topic in recent years. In this regard, it is relevant to generalize the latest achievements in the field of synthesis, properties and application of hyperbranched polyester polyols with terminal oxygen, nitrogen, silicon, sulfur and organophosphorus fragments. The advantage of hyperbranched polyester polyols of the Boltorn H series is their industrial availability, biodegradability, nanoscale, non-toxicity and high solubility in various polar solvents due to short monomer units, as well as the presence of reactive terminal hydroxyl groups. Functionalization of hyperbranched polyester polyols at hydroxyl groups is mainly carried out by addition of acid anhydrides, iso(thio)cyanates, alkenes, lactides, lactones, lactams, epoxy compounds or reactions with halogenated compounds (alkyl halides, acid chlorides). In some cases, for the functionalization of polyester polyols special linkers are used, such as acid chlorides of unsaturated or dicarboxylic acids, diisocyanates, etc., which provide covalent bonding of the hyperbranched polymer with the target functional group. The obtained derivatives of hyperbranched polyesters are widely used in such areas as biomedicine, pharmacy, paints and varnishes, they are also used as catalysts, membranes, multifunctional coatings, plasticizers and polymer stabilizers.

A new adsorbent based on powdered linen cellulose modified with hyperbranched polyester with terminal benzoyl thiocarbamate groups has been synthesized. Complexes with Cu(II) and Co(II) ions have been obtained. The structure of the adsorbent and complexes has been established by IR spectroscopy and potentiometric titration. The adsorption capacity of the adsorbent and conditions for its regeneration from the complexes have been estimated.

A new hybrid adsorbent has been synthesized by covalent linking of activated zeolite with hyperbranched polyester containing 8 terminal N-benzoylthiocarbamate groups. The structure of the polymer ligand was defined by IR, 1H and 13C NMR spectroscopy. The complexing properties of the adsorbent have been studied using the example of complexes with Cu(II) and Co(II) ions. It was proved by IR spectroscopy that N-benzoylthiocarbamate and toluylenecarbamate groups participate in complexation with metal ions. According to electron microscopy and porometry data, the average particle diameter of the adsorbent is 34.56 μm and the mesopore diameter is 4.19 nm. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have shown that the hybrid adsorbent is thermally stable up to 150 °C. The sorption capacities of the adsorbent for Cu(II) and Co(II) ions are 31.92 and 17.7 g/kg. It was shown that the desorption process of metal ions from the complexes occurs in an acidic medium at pH 4 with the regeneration of the original adsorbent.

A new hybrid adsorbent based on zeolite modified with hyperbranched polyesterpolybenzoylthiocarbamate is presented. The structure and morphology of the sorbent are characterized by potentiometric titration, IR, 1H and 13C NMR spectroscopy, and electron microscopy. The fundamental possibility of extracting transition metal ions has been demonstrated using the examples of CuII and CoII ions. It is shown that the sorption capacity of the adsorbent to CuII salt is 25.34 mg g−1. A method of sorbent regeneration is proposed.

Syntheses of a polydentate ligand based on the second-generation hyperbranched polyester containing 3-(2-aminoethyl)amino]propionate groups and its metal complex with copper(II) ions have been elaborated. In view of the IR, electronic absorption, and EPR spectroscopy data, it has been suggested that the coordination sites in the metal-polymer complex are paramagnetic sites with the CuN4Solv2 or CuN2O2Solv2 composition (Solv = H2O, DMSO).

The interaction of Co(NO3)2 and Cu(NO3)2 with hyperbranched polyester containing 7 terminal benzoyl thiocarbamate groups has been studied by IR-Fourier and electron absorption spectroscopy. А new polynuclear complexes of Co(II) and Cu(II) with poly(benzoyl thiocarbamate)-modified hyperbranched polyester have been synthesized. It has been found that the oxygen and sulfur atoms of the peripheral benzoyl thiocarbamate fragments of the macroligand are involved in coordination with metal ions, the metal to ligand ratio being 7 : 1.