Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Structural and magnetic properties of Li2O–Fe2O3 ceramic nanostructures

xLi₂O–(1−x)α-Fe₂O₃ (x=0.1, 0.3, 0.5, and 0.7) nanoparticle systems were successfully synthesized by mechanochemical activation of Li₂O and α-Fe₂O₃ mixtures for 0–12 h of ball milling time. The study aims at exploring the formation of magnetic oxide semiconductors at the nanoscale, which is of crucial importance for catalysis, sensing and electrochemical applications. X-ray powder diffraction (XRD), Mössbauer spectroscopy and magnetic measurements were used to study the phase evolution of xLi₂O–(1−x)α-Fe₂O₃ nanoparticle systems under the mechanochemical activation process. Rietveld refinement of the XRD patterns yielded the values of the particle size as function of composition and milling times and indicated the presence of Li-substituted hematite and tetra lithium iron oxide LiFeO₂, along with the formation of multiple phases for large x values and long milling times. The Mössbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with lithium oxide. Magnetic measurements recorded at 5 K to room temperature (RT) in an applied magnetic field of 50,000 Oe showed that the magnetization of the milled samples is larger at low temperatures than at RT and increases with decreasing particle size. Zero field cooling measurements made possible the determination of the blocking temperatures of the specimens as function of ball milling time and evidenced the occurrence of superparamagnetism in the studied samples. This result correlates well with the observed presence of a quadrupole-split doublet in the Mössbauer spectra.     

Yellow–green organic light-emitting diode based on tris(2-methyl-8-quinolinolate) scandium

Efficient yellow–green electroluminescence emission at λ_max = 530 nm with CIE coordinates x = 0.3913, y = 0.4947 was obtained with organic light-emitting devices based on tris(2-methyl-8-quinolinolate) scandium (1). The device with the configuration of indium tin oxide/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/1/Yb exhibits current efficiency of 3.1 cd/A and power efficiency of 1.8 lm/W at a luminance of 100 cd/m². The DFT calculations demonstrate that structural changes of the scandium complex 1 influence the electroluminescence spectrum, the better agreement with experimental data being achieved when monodentate ligands are taken into consideration.     

Effect of Electrolysis and Heat Treatment Conditions on the Rate of Formation and Magnetic Properties of Very Fine Iron

The effect of electrolysis and heat treatment conditions on the rate of formation and magnetic properties of very fine iron cobalt alloy powder is studied. The optimum conditions for powder preparation are as follows: electrolysis temperature 70°C, heat treatment temperature 500°C, cathode rotation rate 1 rad/sec, cathode current density 2 kA/m², pH = 3.5 ± 0.5, oleic acid concentration 10 kg/m³, electrolyte concentration 20-30 kg/m³, ion ratios of 54:46 and 40:60 for Fe²⁺:Co²⁺.     

2-Mercaptobenzothiazolate complexes of rare earth metals and their electroluminescent properties

We have demonstrated the electroluminescent (EL) properties of 2-mercaptobenzothiazolate complexes of rare earth metals [Ln(mbt)₃, Ln = Y, Sm, Eu, Gd, Tb, Dy, Tm] using simple non-doped two-layer organic light emitting diode with the configuration of indium tin oxide/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/Ln(mbt)₃/Yb. It was found that 2-mercaptobenzothiazolate complexes have highly efficient intra-energy transfer from the singlet to the triplet state of the ligand, and then to the excited state of the central lanthanide ions. Thus Y(mbt)₃ and Gd(mbt)₃ exhibit the broad ligand-centered emission with maximum near 600 nm and Dy(mbt)₃, Tb(mbt)₃ and Tm(mbt)₃ complexes exhibit pure sharp emission bands from the intra f–f transitions of lanthanide ions Tb³⁺: ⁵D₄ → ⁷F₆ (492 nm), ⁵D₄ → ⁷F₅ (547 nm), ⁵D₄ → ⁷F₄ (589 nm), ⁵D₄ → ⁷F₃ (624 nm); Dy³⁺: ⁴F_9/2 → ⁶H_13/2 (575 nm) and Tm³⁺: ³H₄–³H₆ (795 нм).     

Kinase CDK2 in Mammalian Meiotic Prophase I: Screening for Hetero- and Homomorphic Sex Chromosomes

Cyclin-dependent kinases (CDKs) are crucial regulators of the eukaryotic cell cycle. The critical role of CDK2 in the progression of meiosis was demonstrated in a single mammalian species, the mouse. We used immunocytochemistry to study the localization of CDK2 during meiosis in seven rodent species that possess hetero- and homomorphic male sex chromosomes. To compare the distribution of CDK2 in XY and XX male sex chromosomes, we performed multi-round immunostaining of a number of marker proteins in meiotic chromosomes of the rat and subterranean mole voles. Antibodies to the following proteins were used: RAD51, a member of the double-stranded DNA break repair machinery; MLH1, a component of the DNA mismatch repair system; and SUN1, which is involved in the connection between the meiotic telomeres and nuclear envelope, alongside the synaptic protein SYCP3 and kinetochore marker CREST. Using an enhanced protocol, we were able to assess the distribution of as many as four separate proteins in the same meiotic cell. We showed that during prophase I, CDK2 localizes to telomeric and interstitial regions of autosomes in all species investigated (rat, vole, hamster, subterranean mole voles, and mole rats). In sex bivalents following synaptic specificity, the CDK2 signals were distributed in three different modes. In the XY bivalent in the rat and mole rat, we detected numerous CDK2 signals in asynaptic regions and a single CDK2 focus on synaptic segments, similar to the mouse sex chromosomes. In the mole voles, which have unique XX sex chromosomes in males, CDK2 signals were nevertheless distributed similarly to the rat XY sex chromosomes. In the vole, sex chromosomes did not synapse, but demonstrated CDK2 signals of varying intensity, similar to the rat X and Y chromosomes. In female mole voles, the XX bivalent had CDK2 pattern similar to autosomes of all species. In the hamster, CDK2 signals were revealed in telomeric regions in the short synaptic segment of the sex bivalent. We found that CDK2 signals colocalize with SUN1 and MLH1 signals in meiotic chromosomes in rats and mole voles, similar to the mouse. The difference in CDK2 manifestation at the prophase I sex chromosomes can be considered an example of the rapid chromosome evolution in mammals.     

Multiphase Biomineralization: Enigmatic Invasive Siliceous Diatoms Produce Crystalline Calcite

Diatoms are considered unicellular eukaryotic organisms exclusively depositing biogenic silica. Heretofore there has been no report of calcification by these algae. Here it is shown that calcium carbonate within the stalks of Didymosphenia geminata, a nuisance species that has prolifically colonized streams and rivers globally, is biogenic in origin and occurs as a network of calcite nanofibers. The nanofibrous framework in the mineralized polysaccharide matrix imparts mechanical support to the stalks, providing stability in variable flow conditions. The results demonstrate that D. geminata possesses cellular and periplasmic carbonic‐anhydrases that contribute to carbon fixation and biomineralization, respectively. The activity of external carbonic‐anhydrase was more than 50% of the total activity, which points to its role in anchoring this bioeroding diatom on hard surfaces. The first evidence of multiphase biomineralization by diatoms that deposit both biogenic silica and crystalline biogenic calcite which are imparting distinct functional advantage to the organism is provided.     

One‐ and two‐phase isochoric heat capacity measurements of aqueous solution of nacl near the critical point of pure water

Isochoric heat capacities of H₂O+NaCl solutions (0.0031 and 0.0063 mole fraction of NaCl) were measured with a high temperature and high pressure adiabatic calorimeter near the sub‐critical and near the supercritical point of pure water. Temperatures ranged from 361 to 677 K. Measurements were made at six densities, namely: 367.07 and 485.59 kg·m^?3 for x = 0.0031 mol fraction of NaCl and 388.65, 560.03, 607.05, and 973.70 kg·m^?3 for x = 0.0063 mol fraction of NaCl. Measurements were conducted in the two‐and one‐phase regions including near phase transition temperatures T_S(ρ). The phase transition temperatures T_S(ρ) and saturated isochoric heat capacity values C_VX have been determined for each isochore. The uncertainty in heat capacity measurements is estimated to be 3.5% to 4.5% near the phase transition and critical points. Present and previous results of heat capacity measurements were compared with predictions from the crossover (CREOS) and Pitzer—Tanger–Hovey equations of state (PTH EOS). Our previous heat capacity measurements were found to deviate systematically from crossover‐model predictions. The present results show good agreement with the crossover model for the composition x = 0.0031 mol fraction.     

The Effect of a Pulse Current Supply on the Structure and Magnetic Properties of Highly Dispersed Iron

The paper examines how a pulse current supply affects the formation of highly dispersed iron powder particles. We determine the optimum current pulse frequency (10⁴-10³Hz), the ratio of the amplitude of the nucleation current to the amplitude of the crystal growth current (I _n/I _g = 5:25) and the optimum ratio of the nucleation time to the crystal growth time (τ_n/τ_g = 1:10). The effect of the pulsed current manifests itself in decrease in dendricity, i.e., a reduction of the particle anisotropy, and has little impact on the powder dispersity.