Alexander Zhigunov

Self-Assembly of Aniline Oligomers

A great number of nano/microscaled morphologies have recently been prepared during the oxidation of aniline. At the early stage of oxidation, aniline oligomers are obtained, often in spectacular morphologies depending on reaction conditions. Herein, the flower-like hierarchical architectures assembled from aniline oligomers by a template-free method are reported. Their formation process is ascribed to the self-assembly of oligoanilines through non-covalent interactions, such as hydrogen bonding, hydrophobic forces, and π-π stacking. The model of directional growth is offered to explain the formation of petal-like objects and, subsequently, flowers. In order to investigate the chemical structure of the oligomers, a series of characterizations have been carried out, such as matrix-assisted laser desorption ionization, time-of-flight mass spectrometry, gas chromatography coupled with mass spectrometry analysis, X-ray diffraction, and UV/Vis, Fourier-transform infrared, and Raman spectroscopies. Based on the results of characterization methods, a formation mechanism for aniline oligomers and their self-assembly is proposed.

Macromolecular HPMA-based nanoparticles with cholesterol for solid-tumor targeting: detailed study of the inner structure of a highly efficient drug delivery system.

We report a rigorous investigation into the detailed structure of nanoparticles already shown to be successful drug delivery nanocarriers. The basic structure of the drug conjugates consists of an N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer bearing the anticancer drug doxorubicin (Dox) bound via a pH-sensitive hydrazone bond and a defined amount of cholesterol moieties that vary in hydrophobicity. The results show that size, anisotropy, and aggregation number N(aggr) of the nanoparticles grows with increasing cholesterol content. From ab initio calculations, we conclude that the most probable structure of HPMA copolymer-cholesterol nanoparticles is a pearl necklace structure, where ellipsoidal pearls mainly composed of cholesterol are covered by a HPMA shell; pearls are connected by bridges composed of hydrophilic HPMA copolymer chains. Using a combination of techniques, we unambiguously show that the Dox moieties are not impregnated inside a cholesterol core but are instead uniformly distributed across the whole nanoparticle, including the hydrophilic HPMA shell surface.

Structural Diversity of Solid Dispersions of Acetylsalicylic Acid As Seen by Solid-State NMR

Solid dispersions of active pharmaceutical ingredients are of increasing interest due to their versatile use. In the present study polyvinylpyrrolidone (PVP), poly[N-(2-hydroxypropyl)-metacrylamide] (pHPMA), poly(2-ethyl-2-oxazoline) (PEOx), and polyethylene glycol (PEG), each in three Mw, were used to demonstrate structural diversity of solid dispersions. Acetylsalicylic acid (ASA) was used as a model drug. Four distinct types of the solid dispersions of ASA were created using a freeze-drying method: (i) crystalline solid dispersions containing nanocrystalline ASA in a crystalline PEG matrix; (ii) amorphous glass suspensions with large ASA crystallites embedded in amorphous pHPMA; (iii) solid solutions with molecularly dispersed ASA in rigid amorphous PVP; and (iv) nanoheterogeneous solid solutions/suspensions containing nanosized ASA clusters dispersed in a semiflexible matrix of PEOx. The obtained structural data confirmed that the type of solid dispersion can be primarily controlled by the chemical constitutions of the applied polymers, while the molecular weight of the polymers had no detectable impact. The molecular structure of the prepared dispersions was characterized using solid-state NMR, wide-angle X-ray scattering (WAXS), and differential scanning calorimetry (DSC). By applying various (1)H-(13)C and (1)H-(1)H correlation experiments combined with T1((1)H) and T1ρ((1)H) relaxation data, the extent of the molecular mixing was determined over a wide range of distances, from intimate intermolecular contacts (0.1-0.5 nm) up to the phase-separated nanodomains reaching ca. 500 nm. Hydrogen-bond interactions between ASA and polymers were probed by the analysis of (13)C and (15)N CP/MAS NMR spectra combined with the measurements of (1)H-(15)N dipolar profiles. Overall potentialities and limitations of individual experimental techniques were thoroughly evaluated.

Stealth Amphiphiles: Self-Assembly of Polyhedral Boron Clusters

This is the first experimental evidence that both self-assembly and surface activity are common features of all water-soluble boron cluster compounds. The solution behavior of anionic polyhedral boranes (sodium decaborate, sodium dodecaborate, and sodium mercaptododecaborate), carboranes (potassium 1-carba-dodecaborate), and metallacarboranes {sodium [cobalt bis(1,2-dicarbollide)]} was extensively studied, and it is evident that all the anionic boron clusters form multimolecular aggregates in water. However, the mechanism of aggregation is dependent on size and polarity. The series of studied clusters spans from a small hydrophilic decaborate-resembling hydrotrope to a bulky hydrophobic cobalt bis(dicarbollide) behaving like a classical surfactant. Despite their pristine structure resembling Platonic solids, the nature of anionic boron cluster compounds is inherently amphiphilic-they are stealth amphiphiles.

Small‐angle X‐ray scattering and light scattering study of hybrid nanoparticles composed of thermoresponsive triblock copolymer F127 and thermoresponsive statistical polyoxazolines with hydrophobic moieties

A combination of new thermoresponsive statistical polyoxazolines, poly[(2-butyl-2-oxazoline)-stat-(2-isopropyl-2-oxazoline)] [pBuOx-co-piPrOx], with different hydrophobic moieties and F127 surfactant as a template system for the creation of thermosensitive nanoparticles for radionuclide delivery has recently been tested [Panek, Filippov, Hrubý, Rabyk, Bogomolova, Kucka & Stěpanek (2012). Macromol. Rapid Commun. 33, 1683–1689]. It was shown that the presence of the thermosensitive F127 triblock copolymer in solution reduces nanoparticle size and polydispersity. This article focuses on a determination of the internal structure and solution properties of the nanoparticles in the temperature range from 288 to 312 K. Here, it is demonstrated that below the cloud point temperature (CPT) the polyoxazolines and F127 form complexes that co-exist in solution with single F127 molecules and large aggregates. When the temperature is raised above the CPT, nanoparticles composed of polyoxazolines and F127 are predominant in solution. These nanoparticles could be described by a spherical shell model. It was found that the molar weight and hydrophobicity of the polymer do not influence the size of the outer radius and only slightly change the inner radius of the nanoparticles. At the same time, molar weight and hydrophobicity did affect the process of nanoparticle formation. In conclusion, poly(2-oxazoline) molecules are fully incorporated inside of F127 micelles, and this result is very promising for the successful application of such systems in radionuclide delivery.

Facile synthesis of CuO nanosheets via the controlled delamination of layered copper hydroxide acetate

CuO nanosheets were prepared by the controlled delamination of layered copper hydroxide acetate followed by the in situ solvothermal transformation of hydroxide to oxide. The reaction was performed in 1-butanol in order to prevent recrystallization or nanoparticle aggregation. Analyses by small angle X-ray scattering, transmission electron microscopy, and atomic force microscopy revealed that the CuO nanosheets are approximately 1 nm thin, corresponding to three to four stacked CuO6 octahedral layers. The average lateral size is approximately 5 nm. The nanosheets form stable dispersions in 1-butanol that are suitable for the fabrication of transparent and homogeneous CuO thin films by spin-coating or inkjet printing techniques. The present synthesis is a rare example of the top down strategy leading to the nanometric two-dimensional nanosheets of non-layered oxide materials.

Influence of clay-nanofiller geometry on the structure and properties of poly(lactic acid)/thermoplastic polyurethane nanocomposites

The effect of two clays with different geometries, viz. organophilized montmorillonite nanoplatelets (oMMT) and halloysite nanotubes (HNT), on the structure and properties of poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) 80/20 and 70/30 has been studied. The reinforcement of both the components and the blend is higher for oMMT due to its higher specific surface area and aspect ratio. The effect of both nanofillers (NFs) on the structure, reflected in a decrease of the dispersed TPU size, is comparable. A larger effect on the viscosity by oMMT is eliminated by its more marked less favourable localization in the dispersed phase in comparison with HNT. The fact that the toughness of the HNT-containing nanocomposite (NC) is markedly higher (with maximum at 1% HNT) than that with oMMT is in contradiction with PLA NC. The results indicate that the application of nanofillers can lead to a polymer system with a balanced mechanical behaviour. However, a different impact of NFs on the polymer components and interface parameters may also lead to antagonistic effects. The influence of NFs, including their geometry, on the polymer blend is more complex in comparison with single-matrix nanocomposites.

Graphite nanoplatelets-modified PLA/PCL: Effect of blend ratio and nanofiller localization on structure and properties

Structure and properties of poly(lactic acid) (PLA)/poly (ɛ-caprolactone) (PCL) influenced by graphite nanoplatelets (GNP) were studied in dependence on blend composition. Electron microscopy indicates predominant localization of GNP in PCL. GNP-induced changes in viscosity hinder refinement of PCL inclusions, support PCL continuity in the co-continuous system, and lead to reduction of PLA inclusions size without GNP being present at the interface in the PCL-matrix blend. Negligible differences in crystallinity of both phases indicate that mechanical behaviour is mainly influenced by reinforcement and GNP-induced changes in morphology. Addition of 5 parts of GNP leads to ~40% and ~25% increase of stiffness in the PCL- and PLA-matrix systems, respectively, whereas the reinforcing effect is practically eliminated in the co-continuous systems due to GNP-induced lower continuity of PLA which enhances toughness. Impact resistance of the 80/20 blend shows increase with 5 parts content due to synergistic effect of PCL/GNP stacks, whereas minor increase in the blend of the ductile PCL matrix with brittle PLA inclusions is caused by GNP-modification of the component parameters. Results indicate high potential of GNP in preparing biocompatible systems with wide range of structure and properties.

Thermoplastic starch composites with TiO2 particles: Preparation, morphology, rheology and mechanical properties

Composites of thermoplastic starch (TPS) with titanium dioxide particles (mTiO2; average size 0.1μm) with very homogeneous matrix and well-dispersed filler were prepared by a two-step method, including solution casting (SC) followed by melt mixing (MM). Light and scanning electron microscopy confirmed that only the two-step procedure (SC+MM) resulted in ideally homogeneous TPS/mTiO2 systems. The composites prepared by single-step MM contained non-plasticized starch granules and the composites prepared by single-step SC suffered from mTiO2 agglomeration. Dynamic mechanical measurements showed an increase modulus with increasing filler concentration. In TPS containing 3wt.% of mTiO2 the stiffness was enhanced by >40%. Further experiments revealed that the recommended addition of chitosan or the exchange of mTiO2 for anisometric titanate nanotubes with high aspect ratio did not improve the properties of the composites.

Cation-sensitive compartmentalization in metallacarborane containing polymer nanoparticles

Alkaline cations (Li+, Na+ and K+) are introduced as agents suitable to control compartmentalization in metallacarborane-rich nanoparticles of double-hydrophilic block copolymer poly(ethylene oxide)-block-poly(2-alkyloxazoline), PEO–POX. Interaction of the metallacarborane (cobalt bis(dicarbollide) anion) with PEO–POX is based mainly on dihydrogen bonding between metallacarborane boron clusters and the polymer backbone resulting in compact nanoparticles. However, the cations are a crucial factor as to whether interaction with PEO or POX segments is preferred. Changes in the bulk concentration of alkaline cations can thus provoke changes in the inner structure of polymeric nanoparticles, which is accompanied by exchange of boron clusters and alkaline cations like Li+. Because of the biomedical importance of metallacarboranes, their conjugates and also lithium salts, the hybrid nanoparticles can act as stimuli-responsive systems for drug delivery.