Biosensor devices that include hybrid nanostructures as transducer surface modifiers meet current requirements for methods of research and determination of drugs, including antidepressants. Here, we consider the features of amperometric monoamine oxidase biosensors based on screen-printed graphite electrodes modified with nanocomposite consisting of C60/cobalt nanoparticles/amino derivative of a second-generation polyether polyol/chitosan in the determination of the tricyclic antidepressant amitriptyline. The best modifier was selected using transmission electron microscopy, scanning electron microscopy, electrochemical impedance spectroscopy, and differential pulse voltammetry. In the biosensor development, the conditions for applying the composite based on cobalt nanoparticles/amino derivative of polyether polyol to the electrode surface were varied: electrochemical deposition, sequential deposition by the layer-on-layer method, and deposition of a mixture. As an analytical signal of the biosensor, we used the peak of the electrochemical oxidation of hydrogen peroxide, which is formed during the enzymatic oxidation of serotonin under the action of monoamine oxidase. The operating principle of the biosensor is based on the inhibitory effect of amitriptyline on the catalytic activity of immobilized monoamine oxidase. For the selected modifier, the determined concentration range of amitriptyline is 1 × 10–4–1 × 10–8 mol/L and the lower limit of the determined contents is 5 × 10–9 mol/L under optimal operating conditions. Comparison of the results of the amitriptyline determination in a pharmaceutical preparation and urine that were obtained using a monoamine oxidase biosensor and the method of fluorescence polarization immunoassay (dilution of the tracer of 1 : 32, dilution of antibodies of 1 : 128, range of working concentrations from 5 × 10–8 to 5 × 10–9 mol/L), which has proven itself in the determination of medicinal substances, confirmed the correctness of the developed method.
A new cobalt nanoparticles (CoNP) with a core-shell structure were obtained in a matrix of a second generation hyperbranched polyester polyol (BH20). The influence of the molar ratio Co2+ to a BH20 on the nature of stabilization centers of cobalt nanoclusters in the polymer morphology magnetic properties anti-protease activity and hemolytic activity of nanoparticles was studied. The obtained nanoparticles are superparamagnetic and have a blocking temperature of 305 K. Inhibition of the activity of the secretory aspartic protease Candida albicans in the presence of nanoparticles is 58-91%. The hemolytic activity of nanoparticles does not exceed 5%. The data obtained determine the presented cobalt nanoparticles in the matrix of the hyperbranched polyester polyol as a promising nanomaterial with low cytotoxicity for use in medicine and pharmacy.
A bioaffinity-based method for the determination of adrenaline and dopamine involving immobilized renatured DNA incorporated into the amperometric biosensor was developed. With the help of spectrophometry and voltammetry data, it was found that the composition of complexes formed with catecholamines and their stability constants were changing with concentration from [КАL 2 ] to [КА 2 L], where КА – catecholamine, L – base pare, and lg β eff = 10.1–13.5. The high affinity of adrenaline and dopamine to the immobilized renatured DNA molecule was revealed, thereby making it possible to run effective concentration of KA from the analyzed solutions of low concentration including multicomponent fluids. The minimum reporting level was found to be 5.5·10 –9 (adrenaline) and 2.0·10 –8 (dopamin) mol/L, respectively. The proposed method is characterized by high sensitivity, reproducibility (relative accuracy does not exceed 5%), and single determination time shorter than 30 min.
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).
This work presents the procedure for the preparation and the physicochemical characteristics of a new chemically modified sorbent on the basis of a NaX zeolite and hyperbranched polyester polyurethane. The procedure for the preliminary activation of the surface of the zeolite by a solution of NaOH allows optimizing the process of immobilization of hyperbranched polyester polyurethane on the surface of the zeolite. The increase in the sorption capacity of the new chemically modified sorbent with respect to Cu(II) ions in model solutions is proven. The obtained data will allow developing a technology for the sorption extraction of rare earth metal ions from objects of environmental control.
A new water-soluble multidentate ligand based on a second-generation hyperbranched polyester containing 3-(morpholin-4-yl)propionate fragments in the terminal position has been synthesized, and its complex with copper(II) has been obtained. The degree of polyester functionalization with aminopropylmorpholine is 56%.
New hyperbranched polyester polycarboxylic acids containing terminal propanoic and acrylic acid fragments have been synthesized. According to the IR spectral data, the complexation of polydentate hyperbranched polyester polycarboxylic acids with Co(II), Ni(II), and Cu(II) ions involves chelation and bidentate bridging coordination by the terminal carboxy groups. All Co(II), Ni(II), and Cu(II) complexes with the obtained polyester polypropanoic acids are characterized by octahedral geometry of the coordination entity (MO6). The Co(II), Ni(II), and Cu(II) complexes with polyester polyacrylic acids have tetrahedral configuration of the coordination entity (MO4).
Синтезированы новые гиперразветвленные полиэфирополикарбоновые кислоты, содержащие фрагменты пропановой и акриловой кислот в терминальных положениях. По данным ИК спектроскопии, полидентатные гиперразветвленные полиэфирополикарбоновые кислоты характеризуются хелатным и бидентатно-мостиковым типами координации карбоксильных групп по отношению к ионам Со(II), Ni(II), Cu(II). Для всех синтезированных полиэфирополипропионатов Со(II), Ni(II), Cu(II) наблюдается октаэдрическая геометрия координационного узла состава МО. При переходе к полиэфирополиакрилатам Со(И), Ni(II), Cu(II) стабилизируется тетраэдрическая геометрия координационного узла состава МО.
New composite copper nanoparticles stabilized by hyperbranched polyesterpolyols of the second, third, and forth generations have been prepared via chemical reduction at different molar ratios of the precursors. The prepared stabilized copper nanoparticles have exhibited fungicide activity against Penicillium funiculosum, Penicillium ochro chloron, Paecilomyces variotii, Aspergillus niger, Aspergillus oryzae, and Aspergillus terreus strains. Copper nanoparticles stabilized by hyperbranched polyesterpolyols of the second and forth generations are hemocompatible.
Novel polydentate ligands on the basis of second- and third-generation hyperbranched polyesters containing terminal poly[3-(morpholin-4-yl)propionate] groups and their 6 : 1 and 13 : 1 polynuclear copper(II) complexes were synthesized. The degree of functionalization of the polyesters with morpholine increases in going from the second (56%) to third generation (68%). According to IR and electronic spectroscopy data, each coordination entity in the complexes is an isolated paramagnetic center of the formula CuN2O2Solv2 (Solv = H2O, DMSO).
A series of cobalt (Co) and its oxides based nanoparticles were synthesized by using hyperbranched polyester polyol Boltorn H20 as a platform and sodium borohydride as a reducing agent. UV, FT-IR, XRD, NTA, and TEM methods were employed to obtain physicochemical characteristics of the products. The average diameter of Co nanoparticles was approximately 8.2±3.4 nm. Their magnetic properties, including hysteresis loop, field-cooled, and zero field-cooled curves were investigated. The nanoparticles exhibit superparamagnetism at room temperature, accompanied by magnetic hysteresis below the blocking temperature.
The use of hyperbranched polyesterpolyols of different generations favors firmer fixation of carbon nanotubes and silver nanoparticles as components of composite materials on the electrode surface (0.028 mg cm –2 ), which improves the operation characteristics of monoamine oxidase biosensors. The size of silver nanoparticles (18–52 nm) depends on the conditions for preparing hyperbranched polyesterpolyols, and their use as electrode modifiers influences the analytical possibilities of amperometric biosensors. Silver nanoparticles (18 nm, data of atomic force microscopy) in polyesterpolyols of third generation (pH 10.0) as components of the developed biosensors extend the interval of determinable concentrations to 1 × 10 –4 –1 × 10 –8 M and decrease the lower limit of determination to 3 × 10 –9 M, compared to the unmodified sensors, owing to enhancement of the analytical signal. The developed biosensors were tested in monitoring of drugs (antidepressants) in Coaxil and Auroriks drug forms with the relative standard deviation on the level of 0.052.
New polydentate ligands based on hyperbranched second and third generation polyesters containing terminal (3-diethylamino)propionate fragments and their polynuclear copper(II) complexes were synthesized and characterized by spectroscopic methods. The acid-base properties spectroscopy determined that the functionalization degree of the diethylamine-modified hyperbranched polyesters (LI, LII) increases from the second (56%) to third (81%) generation. The polynuclear complexes Cu(II)–LI and Cu(II)–LII were observed. A coordination site of the complexes contains paramagnetic fragment CuN2O2Solv2 where Solv is H2O or DMSO. The hyperbranched poly(ester amine) of the third generation have strong antifungal activity against Aspergillus fumigatus culture, and its metal complex is active against Candida albicans culture.
Novel polydentate ligands were obtained from second and third generation hyperbranched polyesters containing terminal (3-diethylamino)propionate groups. Polynuclear Cu II complexes with these ligands were synthesized. The degree of diethylamination of the polyesters increases when moving from the second to the third generation (from 56 to 81%). In polynuclear complexes, the ratios of Cu to hyperbranched ligand are 6 : 1 and 13 : 1 for second and third generation polyester polyamines, respectively. It was demonstrated using IR and ESR spectroscopy that each coordination polyhedron in the complexes is an isolated paramagnetic center of the formula CuN 2 O 2 Solv 2 (Solv = H 2 O, DMSO).
New amino and carboxy derivatives of methyl 2,2-bis(hydroxymethyl)propionate have been synthesized as models of terminal fragments of hyperbranched polyester polyamines and polyesters polycarboxylic acids, and their spectral characteristics have been studied.
•Research the structure of mixed micelles in binary systems Boltorn H/surfactant.•Investigate the self-organization of binary systems Boltorn H/non-ionic surfactant.•Investigate Orange OT solubilization by mixed micelles Boltorn H/surfactant.•The influence of surfactants on self-organization of the Boltorn H structure.
Doxorubicin fixation by hyperbranched polyester polyol Boltorn H acid derivatives and their binary systems in the presence of a surfactant (Brij-35, Triton X-100) was investigated. Doxorubicin fixation degree nonlinearly depends on the number of acid groups in the polyester polyacid. Polyacid/surfactant binary systems fix up to 60% of doxorubicin from the solution.