Supramolecular Amphiphiles Based on Pillar[5]arene and Meroterpenoids: Synthesis,Self-Association and Interaction with Floxuridine

In recent years, meroterpenoids have found wide biomedical application due to their synthetic availability, low toxicity, and biocompatibility. However, these compounds are not used in targeted drug delivery systems due to their high affinity for cell membranes, both healthy and in cancer cells. Using the approach of creating supramolecular amphiphiles, we have developed self-assembling systems based on water-soluble pillar[5]arene and synthetic meroterpenoids containing geraniol, myrtenol, farnesol, and phytol fragments. The resulting systems can be used as universal drug delivery systems. It was shown by turbidimetry that the obtained pillar[5]arene/synthetic meroterpenoid systems do not interact with the model cell membrane at pH = 7.4, but the associates are destroyed at pH = 4.1. In this case, the synthetic meroterpenoid is incorporated into the lipid bilayer of the model membrane. The characteristics of supramolecular self-assembly, association constants and stoichiometry of the most stable pillar[5]arene/synthetic meroterpenoid complexes were established by UV-vis spectroscopy and dynamic light scattering (DLS). It was shown that supramolecular amphiphiles based on pillar[5]arene/synthetic meroterpenoid systems form monodisperse associates in a wide range of concentrations. The inclusion of the antitumor drug 5-fluoro-2′-deoxyuridine (floxuridine) into the structure of the supramolecular associate was demonstrated by DLS, 19F, 2D DOSY NMR spectroscopy.     

Isotactic and syndiotactic polypropylene/multi-wall carbon nanotube composites: synthesis and properties

Isotactic polypropylene (iPP) and syndiotactic polypropylene (sPP) nanocomposites containing 0.1–3.5 wt.% multi-wall carbon nanotubes (MWCNTs) have been synthesized via in situ polymerization method with the use of C₂- and C_s- symmetry zirconocenes activated by methylaluminoxane (MAO) in liquid propylene medium. Fracture morphology studies by SEM reveal different MWCNT dispersion efficiency in various polymer matrices, which arises from the catalytic peculiarities of the composite synthesis. Considerable Young’s modulus enhancement of iPP and sPP (25–66%) takes place even at low MWCNT loadings (below 0.5 wt.%). The obtained nanocomposites can find use as efficient electromagnetic shielding materials and microwave absorbing filters due to relatively low permittivity values and considerable dielectric losses in microwave range. Calorimetry data demonstrate that MWCNTs exert evident influence as nucleating agents causing the rise of iPP and sPP crystallization temperature. Considerable retardation effect on iPP thermal oxidative degradation has been observed: the temperature of maximal weight loss rate rises by ~52 °C upon incorporating only 1.4 wt.% MWCNTs.     

Multi-physics modeling of doxorubicine binding to ion-exchange resin in blood filtration devices

A group of drugs used in intra-arterial chemotherapy (IAC) have intrinsic ionic properties, which can be used for filtering excessive drugs from blood in order to reduce systemic toxicity. The ion-exchange mechanism is utilized in an endovascular Chemofilter device which can be deployed during the IAC for capturing ionic drugs after they have had their effect on the tumor. In this study, the concentrated solution theory is used to account for the effect of electrochemical forces on the drug transport and adsorption by introducing an effective diffusion coefficient in the advection–diffusion–reaction equation. Consequently, a multi-physics model coupling hemodynamic and electrochemical forces is developed and applied to simulations of the transport and binding of doxorubicine in the Chemofilter device. A comparison of drug adsorption predicted by the computations to that measured in animal studies demonstrated the benefits of using the concentrated solution theory over the Nernst–Plank relations for modeling drug binding.     

Complex formation of methylcellulose with poly(acrylic acid)

Complex formation between poly(acrylic acid) and methylcellulose in aqueous solutions has been studied by viscometric and turbidimetric methods. The critical pH values in their dependence of polymer concentration were determined. The influence of the nature of a nonionic polymer on the composition and stability of interpolymer complexes is shown. The phase behaviour of acrylic acid‐graft‐methylcellulose copolymer in aqueous solutions is analysed from their complexation point of view. © 2000 Society of Chemical Industry     

Cluster-associate viscosity model of tin chloride in comparison with the Frenkel model

Determining the viscosity of inorganic molten compounds like tin chloride is critically important for material processing, chemical synthesis, and energy applications. However, experimental limitations have restricted the development of accurate viscosity models. This study tests a new cluster-associate model for predicting the viscosity of molten tin chloride across a wide temperature range. The model links viscosity to the structure and dynamics of molecular clusters in the melt. The aim of this study is to establish a correlation between viscosity and cluster formation within a liquid, using tin chloride as an example. The data were calculated using a newly developed equation based on the concept of randomized particles. The temperature range studied was from the melting point to the boiling point. To verify the accuracy of the cluster-associate model, it was compared with the Frenkel equation using logarithmic coordinates. Simulations were performed on tin chloride, which yielded results showing a linear relationship between the degree of cluster association and the activation energy of fluidity. The proportionality coefficient reflects the activation energy associated with a single cluster. The Frenkel equation in the logarithmic coordinate scale was compared with the cluster-associate model. The functional dependence and correspondence of these models are indicated by their high coefficient mutual correlation. The proposed viscosity model underwent testing for the entire liquid state range of the substance, and calculations confirmed its validity. This enables reliable use of the suggested model for both high- and low-temperature extrapolation, including the critical point region.     

A transparent hybrid of nanocrystalline cellulose and amorphous calcium carbonate nanoparticles

Nanocellulose hybrids are promising candidates for biodegradable multifunctional materials. Hybrids of nanocrystalline cellulose (NCC) and amorphous calcium carbonate (ACC) nanoparticles were obtained through a facile chemical approach over a wide range of compositions. Controlling the interactions between NCC and ACC results in hard, transparent structures with tunable composition, homogeneity and anisotropy.     

The effect of multiple martensitic transformations on diffusion of Fe and Ni atoms in Fe-31.7%Ni-0.06%C alloy

Diffusion characteristics of iron and nickel atoms were investigated using radioactive isotopes method in phase-hardened metastable iron-nickel Fe-31.7%Ni-0.06%C alloy with nanofragmented structure. It has been found that diffusion mobility of nickel and iron atoms in reverted austenite of Fe-31.7%Ni-0.06%C alloy significantly increases as the result of multiple γ-α-γ martensitic transformations. The diffusion coefficients of nickel and iron in the austenite at 400°C corresponded to the stationary diffusion coefficients at the temperatures above 900°C. The revealed diffusion acceleration at low temperatures is caused by high-density dislocations and additional low-angle subboundaries of disoriented nanofragments of reverted austenite and deformation twin subboundaries formed during multiple γ-α-γ cycles.