New monomers of the biquinoline series—diyldimethanamines—have been synthesized, and polymers having biquinoline units in the main chain and their metal–polymer complexes with cuprous chloride have been obtained using these monomers. The resulting starting compounds and polymers have been studied using NMR spectroscopy, HPLC, and simultaneous thermal (thermogravimetric and differential thermal) analysis, and the mechanical characteristics of the polymers and metal–polymer complexes have been examined. It has been shown that the structure and physicochemical properties of the polymers based on synthesized diyldimethanediamines largely depend on the position of groups in the biquinoline moiety and the presence of interchain coordination bonds in the polymer.
Planar chromatography is used to develop methods for the analytical control of processes of the synthesis of biomedical polymers and their complexes with biologically active substances, which made it possible to create a number of long-acting antiviral, antitumor, antimicrobial, and antiseptic preparations.
A method for the synthesis of new bifunctional biquinoline monomers, 2,2′-biquinoline-6,6′-, 7,7′-, and 8,8′-dicarboxylic acids, was developed. Copolyamic acids and copolybenzoxazinoneimides with biquinoline units in the main chain and their metalpolymer complexes with Cu I were synthesized, and their mechanical, thermal, molecular, and electrochemical properties were studied.
A method for determination of residual monomers in homo-and copolymers of acrylamide and N,N,N-trimethyl-N-methacryloyloxyethylammonium methylsulfate by means of thin-layer chromatography has been developed. Efficient eluting systems have been found for separation and identification of the indicated components, and the limits of their quantitative determination in the obtained polymers have been established.
Синтезировали сополимер с молекулярной массой 45 кДа, содержаний 7 мол.% звеньев виниламина, 80 мол.% винилпирролидона и 3 мол.% звеньев винилиминодиуксусной кислоты. Методом высокоэффективной эксклюзионной жидкостной хроматографии исследовали его комплексообразование с ионом Ga 3+ . Дана характеристика металл-полимерного комплекса методами эксклюзионной хроматографии и спектральными методами (ИК, 1 Н ЯМР). Комплекс имел мономолекулярную структуру, где ион металла играл роль анкерного фрагмента между звеньями винилиминодиуксусной кислоты и был стабилен в реакции интерлигандного обмена с гистидином.
A terpolymer with a molecular weight of 45 kDa containing 7 mol % of vinylamine units, 80 mol % of vinylpyrrolidone, and 3 mol % of vinyliminodiacetic acid units has been synthesized. Its complexation with Ga3+ ion has been studied by HPLC. The resulting metal–polymer complex has been characterized by exclusion chromatography and spectral (IR, 1H NMR) data. The complex has a monomolecular structure where the metal ion acts as an anchor fragment between vinyliminodiacetic acid units and is stable in the reaction of interligand exchange with histidine.
The method for preparation of copolymers of N-vinylpyrrolidone (VP) and N-vinylamine (VA) with high yield were developed; the method involves radical copolymerization of VP with N-vinylformamide(VFA) followed by the removal of formyl protecting group in the presence of inorganic acids. The optimal conditions for synthesis of copolymers with predefined compositions and molecular masses were determined. The influence of temperature, concentrations of reactants, and the nature of an acid on the rate of formyl group removal was estimated. Spectral and chromatographic methods of analytical control of the contents of residual monomers and formic acid (which forms during acidic hydrolysis of the copolymer) were developed.
Terpolymers with a molecular weight of 65 and 13 kDa containing 90 mol.% of N-vinylpyrrolidone, 7 mol.% of N-vinylformamide, and 3 mol.% of N-vinyliminodiacetic acid units have been synthesized. Diethyldithiocarbamate and benzyldithiocarbamate have been used as coligands. The mixed-ligand complexation with Ga3+ ion has been studied by HPLC. The composition and structure of the resulting metal-polymer complexes have been determined by exclusion chromatography and spectral (IR, 1H NMR) data.
Chromatographic methods of analysis of the products of the radical copolymerization of random copolymers of N-vinyl-2-pyrrolidone and 6-crotonoyl aminohexanoic acid are developed and molecular characteristics of the copolymers are determined. A method is proposed for the purification of the obtained carboxylated water-soluble copolymers of monomeric hydrophobic acid impurities by low-pressure gel-permeation chromatography.
The method for analysis of transition metal ions (Zn(II), Cu(II), Со(II), Ni(II), Fe(III)) by high-performance planar (thin layer) chromatography with the use of sorbents modified by chelating fragments of iminodiacetic acid was developed. The correlation between retention factor (Rf) and physico-chemical parameters of the separated systems was studied. It was demonstrated that unlike the pH value, ionic strength of a solution does not exert significant influence on resolution and mobility of transition metal cations
Synthetic methods for random copolymers of N-vinylpyrrolidone and 6-crotonoyl aminohexanoic acid (6-CAHA) were developed. These carboxyl-containing water-soluble copolymers are the promising drug carriers. The technique for purification of polymers of this type from admixed comonomer (hydrophobic 6-CAHA) was proposed. Molecular masses, sizes, and molecular mass distributions were determined by HPLC, optical and hydrodynamic methods.
The exclusion mechanism of the separation of poly(N-vinylformamide) and its derivatives with a cysteamine terminal group in gel permeation chromatography implemented by the suppression of polyelectrolyte swelling and the electroexclusion of macromolecules was established by the transport analytical methods of molecular hydrodynamics (HPLC, velocity sedimentation, and intrinsic viscosity). Based on an analysis of the hydrodynamic characteristics and molecular weights of polymer fractions determined by velocity sedimentation, it was found that the molecular characteristics and polydispersity of the water-soluble poly(N-vinylamide) s of aliphatic carboxylic acids and their derivatives can be calculated with the use of the Benoit universal calibration dependence.
Structural, molecular, and hydrodynamic characteristics of thermostable functionalized polymers [polyamic acids (PAAs) with biquinoline chelate groups in the main chain] were studied by high-performance liquid chromatography. Size exclusion mechanism of chromatography in conditions including suppression of polyelectrolyte swelling and ion-exclusion effects was proved. The influence of molecular and structural characteristics of PAAs on their ability to form metal–polymer complexes (MPCs) with copper(I) chloride was studied. The critical polymer concentration at which binding of two PAA macromolecules with Cu+ ion takes place to form MPCs was estimated.
Recently published data on the separation and quantification of natural nucleosides and some of their derivatives by thin-layer chromatography on silica gel have been summarized. The use of more than 20 mobile systems for the separation of more than 52 nucleosides and derivatives was discussed; in a few cases, the conditions for their densitometry quantitative analysis after TLC separation were considered. The works performed at GosNIIgenetika on the determination of inosine, thymidine, and acadesine with domestic Sorbfil plates were reviewed in detail.
A fast and efficient method of separation of radioactive metal isotopes (99mTc, 161Tb, 68Ga) and synthetic biologically active water-soluble copolymers of the class of N-vinylamides is developed using HPLC on ultrashort monolithic CIM (Convective Interaction Media) columns at the interface. It is shown that, under conditions of elution in aqueous media, the polymers are not separable by molecular weights and structures, but they are well-separable from metal ions. Radioactivity sorption on monolithic sorbents is insignificant, allowing series of experiments to be expressively performed for an optimization of conditions of radiochemical synthesis and routine analysis of radiopharmaceutical preparations.
Poly-N-vinylpyrrolidone derivatives with attached iminodiacetic groups were prepared in a wide range of molecular masses (9 000 - 30 000 Da). Labeling of polymer carrriers with the "cold" Re(CO)(3)(+) species were performed under mild conditions. Metallo-polymeric conjugates were comprechensively characterized by means of spectroscopic methods (IR, NMR, ESI-MS) and also with HPLC. Special attention was payed to the choice of stationary and liquid phases for HPLC procedure, because it is extremally important for the further analysis of radiolabeled polymeric systems.
Multicentered initiators for the controlled (pseudoliving) radical polymerization are synthesized via polymer analog transformation of hydroxyl-containing polyimides based on o-aminophenols. Conditions providing variations in the degree of functionalization of polyimides by initiating 2-bromoisobutyrate groups are determined, and optimum conditions for the preparation of macroinitators containing the above groups in each repeat polyimide unit are found. Via the method of controlled radical polymerization with the atom transfer on multicentered macroinitiators in the presence of complexes of univalent copper halides, graft copolymers of poly(methylmethacrylate) on polyimide backbone are obtained. Molecular-mass characteristics of graft copolymers are studied via multiple-detection size-exclusion liquid chromatography. Preparation of graft copolymers (polymer brushes) with a homogeneous grafting density and a homogeneous length of side chains necessitates grafting of the side chain on the polyimide initiator, which contains initiating groups in each repeat unit.