Magnetic Fractions of PM2.5, PM2.5-10, and PM10 from Coal Fly Ash as Environmental Pollutants.

Characterization of magnetic particulate matter (PM) in coal fly ashes is critical to assessing the health risks associated with industrial coal combustion and for future applications of fine fractions that will minimize solid waste pollution. In this study, magnetic narrow fractions of fine ferrospheres related to environmentally hazardous PM2.5, PM2.5-10, and PM10 were for the first time separated from fly ash produced during combustion of Ekibastuz coal. It was determined that the average diameter of globules in narrow fractions is 1, 2, 3, and 7 µm. The major components of chemical composition are Fe2O3 (57-60) wt %, SiO2 (25-28 wt %), and Al2O3 (10-12 wt %). The phase composition is represented by crystalline phases, including ferrospinel, α-Fe2O3, ε-Fe2O3, mullite, and quartz, as well as the amorphous glass phase. Mössbauer spectroscopy and magnetic measurements confirmed the formation of nanoscale particles of ε-Fe2O3. Stabilization of the ε-Fe2O3 metastable phase, with quite ideal distribution of iron cations, occurs in the glass matrix due to the rapid cooling of fine globules during their formation from mineral components of coal.

Re-entrant cholesteric phase in DNA liquid-crystalline dispersion particles.

In this research, we observe and rationalize theoretically the transition from hexagonal to cholesteric packing of double-stranded (ds) DNA in dispersion particles. The samples were obtained by phase exclusion of linear ds DNA molecules from water-salt solutions of poly(ethylene glycol)-PEG-with concentrations ranging from 120 mg ml-1 to 300 mg ml-1. In the range of PEG concentrations from 120 mg ml-1 to 220 mg ml-1 at room temperature, we find ds DNA molecule packing, typical of classical cholesterics. The corresponding parameters for dispersion particles obtained at concentrations greater than 220 mg ml-1 indicate hexagonal packing of the ds DNA molecules. However, slightly counter-intuitively, the cholesteric-like packing reappears upon the heating of dispersions with hexagonal packing of ds DNA molecules. This transition occurs when the PEG concentration is larger than 220 mg ml-1. The obtained new cholesteric structure differs from the classical cholesterics observed in the PEG concentration range 120-220 mg ml-1 (hence, the term 're-entrant'). Our conclusions are based on the measurements of circular dichroism spectra, X-ray scattering curves and textures of liquid-crystalline phases. We propose a qualitative (similar to the Lindemann criterion for melting of conventional crystals) explanation of this phenomenon in terms of partial melting of so-called quasinematic layers formed by the DNA molecules. The quasinematic layers change their spatial orientation as a result of the competition between the osmotic pressure of the solvent (favoring dense, unidirectional alignment of ds DNA molecules) and twist Frank orientation energy of adjacent layers (favoring cholesteric-like molecular packing).

Effect of Sterical Shielding on the Redox Properties of Imidazoline and Imidazolidine Nitroxides.

The oxidant properties of the series of 2,2,5,5-tetraalkyl imidazoline and imidazolidine nitroxides were investigated. An increase in the number of bulky alkyl substituents leads to a decrease in the rate of reduction with ascorbate, which makes the electrochemical reduction potential more negative and shifts the equilibrium in the mixture of nitroxide and reference hydroxylamine (3-carboxy-1-hydroxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl-1-(15)N) toward the starting compounds. The effect of structural factors on these reactions was analyzed by means of multiple regression using the Fujita steric constant Es and the inductive Hammett constant σI. Satisfactory statistical outputs were obtained in all of the biparameter correlations, denoting that the oxidant properties of the nitroxides are determined by steric and electronic effects of the substituents. The data imply that bulky substituents can stabilize nitroxide and/or destabilize hydroxylamine.

Design of liposome-based pH sensitive nanoSPIN probes: nano-sized particles with incorporated nitroxides.

Liposome-based nanoSized Particles with Incorporated Nitroxides, or nanoSPINs, were designed for EPR applications as pH probes in biological systems. Phospholipid membrane of the liposomes with incorporated gramicidin A showed selective permeability to a small analyte, H(+), while protecting entrapped sensing nitroxide from biological reductants. An application of the pH-sensitive nanoSPIN in an ischemia model in rat heart homogenate allows for monitoring ischemia-induced acidosis while protecting encapsulated nitroxide against bioreduction.

Particles of liquid-crystalline dispersions formed by (nucleic acid-rare earth element) complexes as a potential platform for neutron capture therapy.

Microscopic size particles of the cholesteric double-stranded DNA (RNA) liquid-crystalline dispersions, containing the ions of the rare earth elements in their content, have been obtained for the first time. The properties of these particles differ from those of classical DNA cholesterics noticeably. The local concentration of the rare earth elements in a particle reaches 200 mg/ml. The particles of the liquid-crystalline dispersion of the (DNA-gadolinium) complex maintain the properties for a long time. The combination of the microscopic size of particles, high concentration of gadolinium in particles and their stability opens a way to practical application of this new biomaterial.