V. V. Spiridonov

Noncovalent columnar structures based on β-cyclodextrin

A new method for the synthesis of associates of cyclodextrins (CDs) of the columnar type consisting of the precipitation of CDs from aqueous solutions into acetone at lowered temperatures is developed. It is shown that columnar structures exist in both a crystalline state and in aqueous solutions. Hydrodynamic radii and molecular masses of noncovalent columnar structures (NCSs) in aqueous solutions are determined by the dynamic and static light scattering methods. The degree of association of noncovalent columnar polymers is ∼40. It is revealed the NCS associates based on β-CD are stable and their hydrodynamic radius Rh is equal to 100 ± 10 nm. The kinetics of interactions of initial β-CD and NCS with poly(propylene oxide) (PPO) is studied. The pattern of kinetic curves of Rh growth upon interaction between NCS and PPO indicates that the aggregation of the particles of polymer inclusion complex proceeds in the regime of reaction-limited cluster-cluster aggregation. Kinetic curves describing the interaction processes between β-cyclodextrin and PPO are characterized by the presence of induction period t0. At t > t0, Rh ∞ t0.56 which is typical for the diffusion-limited cluster-cluster aggregation. Schemes of the formation of polymer inclusion complexes between initial β-CD or NCS and poly(propylene oxide) are proposed. Comparison of kinetic data on the complexation of β-CD in solution in the form of associates of two types with PPO demonstrates that columnar forms of associates are reactive species acting as macroreceptors.

Aggregation of Inclusion Complexes Formed by Noncovalent Columnar Structures Based on α- and γ-Cyclodextrins and Poly(alkylene glycols)

Kinetic analysis of the aggregation of complexes formed by columnar types of α- and γ-cyclodextrins (α-CDcol and γ-CDcol) and poly(alkylene glycols) is performed by the dynamic light scattering method. For comparison, analogous studies were conducted for systems containing initial α- and γ-cyclodextrins (α-CD and γ-CD). Upon the aggregation of systems containing α-CD, the number of nuclei with critical sizes slowly increases at the initial part of kinetic curve throughout the solution bulk; when some limiting concentration and sizes of formed aggregates are achieved, the system is transformed into the gel-like state. The aggregation of γ-CDcol-poly(ethylene glycol) system proceeds into two stages. At the first fast stage, aggregates are formed by particles representing single-strand inclusion complexes composed of one γ-CDcol molecule and two units of ethylene oxide. At the second, much slower stage, aggregates are formed by two-strand complexes composed of one γ-CDcol molecule and four units of ethylene oxide. It follows from the comparison of aggregative properties of γ-CDcol-poly(ethylene glycol) and γ-CDcol-poly(propylene glycol) systems that the rate of aggregation is much higher in the second case.

The one-step synthesis of polymer-based magnetic γ-Fe2O3/carboxymethyl cellulose nanocomposites

A novel one-step procedure is described for synthesizing water soluble biocompatible nanocomposites from maghemite nanoparticles and carboxymethyl cellulose (CMC). The procedure allows the magneto-sensitive nanocomposites with a controlled content of the inorganic phase. The maghemite formation has been proved by X-ray diffraction analysis and Mossbauer spectroscopy. An average diameter of the maghemite nanoparticles is equal to 11nm according to transmission electron microscopy. As shown by FTIR spectroscopy, the nanoparticles bind to the polymer matrix via electrostatic and coordination interactions. The diameter of the nanocomposites in dilute aqueous solutions vary from 50nm at the iron content of 2-4.3wt.% to 140nm at the iron content of 5.2-8.6wt.%. The study of specific magnetization of the nanocomposites vs. applied magnetic field indicates their ferromagnetic properties. The saturation magnetization and coercive force of the sample with the maximum maghemite content (8.6wt.%) are 11.5emu/g and 30.08Oe, respectively. The nanocomposite motion has been shown to be controlled by an external magnetic field. The biocompartible maghemite-CMC nanocomposites seem to be promising for encapsulation and delivery of biologically active compounds.

Water-Soluble Magnetic Nanocomposites Based on Carboxymethyl Cellulose and Iron(III) Oxide

The one-step synthesis of water-soluble composites from maghemite (γ-Fe2O3) nanoparticles with a diameter of 12 ± 4 nm and a biocompatible polysaccharide, namely, sodium salt of carboxymethyl cellulose, is described. The role of the polymer matrix consists in stabilization of the resulting nanoparticles by the electrostatic interaction of polymer carboxyl groups with the surface atoms of iron in the (3+) oxidation state. The dissolution of the composites in water affords aggregatively stable dispersions responding to the external magnetic field. The content of the magnetic phase (iron oxide) in the formulation of the maghemite–carboxymethyl cellulose composite is defined by the ratio of components during the synthesis.

Inhibitory effect of polyethylene oxide and polypropylene oxide triblock copolymers on aggregation and fusion of atherogenic low density lipoproteins

Triblock copolymers of poly(ethylene oxide) and poly(propylene oxide) (so-called pluronics) were shown to influence the aggregation and fusion of atherogenic low density lipoproteins (atLDL) and be able to inhibit these processes. The character of the influence and the degree of the stabilizing effect depended on the structure, relative hydrophobicity, and concentration of the copolymer. Pluronics L61, P85, and L64 characterized by the hydrophilic–lipophilic balance (HLB) value from 3 to 16 had the greatest ability to suppress the aggregation of atLDL. Pluronic L81 with the higher hydrophobicity (HLB = 2) partially inhibited atLDL aggregation at low concentrations but stimulated it at high concentrations. The influence of pluronics did not have a direct connection with their ability for micelle formation, but it was realized through individual macromolecules. We suppose that effects of pluronics could be due to their interaction with the lipid component of LDL and to a possible influence of these copolymers on the structure and hydrophilic–lipophilic characteristics of lipoproteins.

Iron-containing nanoparticles based on the 2-hydroxypropyl-β-cyclodextrin in aqueous solutions

The water-soluble hybrid nanoparticles based on high-substituted 2-hydroxypropyl-β-cyclodextrin were formed in situ during the reduction of iron(+2) salts by hypophosphite ion in alkaline medium. These nanoparticles are high sensitive to temperature and ultrasonication. It was established that the temperature and ultrasonication time of exposure increase leads to the successive dissociation of the nanoparticles.

Metal-free thermally-responsive pseudohybrid nanoparticles based on 2-hydroxypropyl-β-cyclodextrin

Pseudohybrid nanoparticles of 800 nm in diameter based on self-assembled high-substituted 2-hydroxypropyl-β-cyclodextrin fabricated in the presence of iron(II) salts were found to be thermally responsive within narrow range of temperature. As-prepared metal-free nanoparticles are stable in aqueous solution at room temperature. However, the increase in temperature results in break-like collapse of nanoparticles to yield species of 400 nm in diameter. On the example of phenolphthalein, it was shown that nanoparticles loaded with model drug decompose to release superficial guest-host inclusion complexes. Local hyperthermia provokes nanoparticles decomposing and drug releasing that allows recognizing focuses of pathology in human body. It might be used for diagnostic medicinal aims and be also considered as basis for the construction of intravascular drug delivery/release systems.

Estimation of the molecular weights of noncovalent columnar polymers based on β-cyclodextrin by the measurement of the aggregation rate of their polymer inclusion complexes with polypropylene glycol

Noncovalent columnar polymers (NCPs) based on cyclodextrins (CD) are polymeric assemblies of molecules that have continuous hollow channels, the width of which is determined by the diameter of the cavity of the initial CDs. The repeating fragment in an NCP is the CD molecule. For NCPs that were obtained by the exclusion of polymer backbone macromolecule from the corresponding inclusion complexes (ICs) based on β-cyclodextrin (NCPexcl), the polymer length, expressed as the number of macrocycles in a single chain (n) is determined by the size of the included ligand, polypropylene glycol (PPG), and is the PPG polymerization degree divided by two. The determination of the molecular weight of an NCP obtained by the precipitation method (NCPprec) is rather difficult, since they are present in the aggregated state rather than in the form of individual molecules in solution. To estimate the molecular weight of NCPprec, an indirect method is used, which is based on the determination of the aggregation rate of the ICs formed as a result of the interaction between an NCP and polypropylene glycol with a fixed molecular weight (MW), in this case PPG 1000. The comparison of the aggregation rates of the inclusion between NCPexcb (which were synthesized using PPGs with different molecular weights) and PPG 1000 with the aggregation rate of the inclusion complex on the basis of NCPprec provided the estimation for the MWs of single polymer chains. The fact that the samples of NCPprec contain ∼30% of the monomeric β-CD was taken into account when constructing the calibration curve. It was demonstrated that the MW of the polypropylene glycol corresponding to NCPprec is 1320 Da. Consequently, ∼11–12 molecules of β-CD are included in the single chains of NCPprec.