Encapsulation of inorganic particles via miniemulsion polymerization. I. Dispersion of titanium dioxide particles in organic media using OLOA 370 as stabilizer

The dispersion of hydrophilic and hydrophobic titanium dioxide (TiO₂) particles in organic media (styrene and cyclohexane) was studied to evaluate the effect of dispersion quality (i.e., size and stability) on the encapsulation efficiencies of subsequent miniemulsion polymerizations. Through screening studies of various block copolymers, OLOA 370 (polybutene–succinimide pentamine) was chosen as the stabilizer for detailed dispersion studies on both types of TiO₂ particles. As a result of strong interactions between the amine end group of the OLOA 370 stabilizer and the hydroxyl groups on the surface of the hydrophilic TiO₂ particles, a good dispersion stability and small particle size (D_v = 39–45 nm) was obtained using 1.0 wt % stabilizer and 20 min of sonification. The dispersions of the hydrophobic TiO₂ particles resulted in a larger average particle size (D_v = 60 nm) and poorer stability. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4419–4430, 2000     

Bias field induced impedance relaxation of TlGaSe2 semiconducting layered crystal at room temperature

Complex Impedance Spectroscopy has been employed for the study of absorption kinetics at TlGaSe₂ layered crystal under Bias voltage at room temperature. Two relaxations mechanisms have been observed. The crystal has “slow” and “fast” relaxation mechanisms in low and high frequency region, respectively. The complex impedance spectra were fitted by the superposition of two Cole‐Cole types of relaxations. The fast relaxation in the higher frequency region may be due to dipolar relaxation and the slow relaxation in the low frequency region may be due to Maxwell‐Wagner type relaxation. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Genomagnetic electrochemical assays of DNA hybridization

An electrochemical genomagnetic hybridization assay has been developed to take advantage of a new and efficient magnetic separation/mixing process, the amplification feature of enzyme labels, and single-use thick-film carbon transducers operated in the pulse-voltammetric mode. It represents the first example of coupling a magnetic isolation with electrochemical detection of DNA hybridization. The new protocol employs an enzyme-linked sandwich solution hybridization, with a magnetic-particle labeled probe hybridizing to a biotinylated DNA target that captures a streptavidin-alkaline phosphatase (AP). The alpha-naphthol product of the enzymatic reaction is quantitated through its well-defined, low-potential (+0.1 V vs. Ag/AgCl) differential pulse-voltammetric peak at the disposable screen-printed electrode. The efficient magnetic isolation is particularly attractive for electrical detection of DNA hybridization which is commonly affected by the presence of non-hybridized nucleic acid adsorbates. The new biomagnetic processing combines such magnetic separation with a low-volume magnetic mixing, and allows simultaneous handling of 12 samples. The attractive bioanalytical behavior of the new enzyme-linked genomagnetic electrical assay is illustrated for the detection of DNA segments related to the breast-cancer BRCA1 gene.     

Ureasulfonamide Polymeric Sorbent for Selective Mercury Extraction

A new polymeric resin with sulfonamide pendant functions has been prepared for the selective extraction of mercuric ions. This polystyrene sulfonamide urea resin with a 3.5 mmol/g total nitrogen content is able to selectively sorb mercury from aqueous solutions. The mercury sorption capacity of the resin is around 1.60 mmol/g under non-buffered conditions. The experiments performed under identical conditions with some metal ions reveal that Cd(II), Pb(II), Zn(II), and Fe(III) ions are also extractable in low quantity (0.05–0.1 mmol/g). The sorbed mercury can be eluted by repeated treatment with hot acetic acid without hydrolysis of the amide groups.     

The formation of a metallosupramolecular porous helicate through salicylaldehydethiosemicarbazone: Synthesis,Characterization, Cytotoxic activity,DNA binding and DFT calculations

The reaction of salicylaldehyde‐S‐methylisothiosemicarbazone in the presence of ethylenediamine base and iron (III)chloride generated unforeseen homotopic dinuclear triple‐stranded iron (III)helicate. The synthesized helicate was characterized by elemental analysis, IR, UV–Vis spectroscopy, magnetic moment measurement, and evaluated cytotoxic activities against K562, HL‐60 and THP‐1 leukemia cells. In addition, solid‐state structure has been determined by single‐crystal X‐ray diffraction technique. In the complex, three dinucleating O, N, N, O donor ligands provide three diazine (═N─N═) bridges between the metal ions and facial O₃N₃ coordination spheres around them. The ligands are folded about the N ─ N single bond and coordinated to the two metal ions in a helical fashion to form the triple helical structure. In the crystal lattice, chains of centrosymmetric rings, which are connected to one another via π─π stacking interactions, are generated by C─H···O intermolecular interactions. The results are also confirmed by the density functional theory (DFT) calculations. The results obtained from the cytotoxicity test showed to be effective in low concentrations on the leukemia cells. An intercalative binding mode of helicate‐DNA complex was confirmed with the high intrinsic binding constant (K_b = 8×10⁶ M^?1) and competitive displacement assay of Ethidium bromide with high Ksv value.     

Synthesis, Metal Complexation and Spectroscopic Characterization of Three New Azo Compounds

The synthesis of azo compounds [4-(N'-2-thiazol-2-ylsulfanyl)-4'-hydroxyazo benzene (1), 4-(N'-2-thiazol-2-ylsulfanyl)-2'-hydroxy-5-tert-butylazobenzene (2), 7-[4-(N'-2-thiazol-2-ylsulfanyl)phenylazo-8-hydroxy quinoline (3)] have been carried out by reacting phenol, 4-tert-butyl phenol and 8-hydroxy quinoline with N'-2-thiazol-2-ylsulfanylamide as coupling component. The resulting ligands (2 and 3) were treated with two transition metal salts (e.g., CuCl₂2H₂O andNiCl₂6H₂O). Cu(II) and Ni(II) complexes of the azo derivative ofphenol were obtained and characterised by IR, UV-Vis, ¹H NMR, spectroscopic and elemental analysis techniques. All the complexes have a metal : ligand ratio of 1 : 2 and are square-planar.     

Speciation and preconcentration of inorganic antimony in waters by Duolite GT-73 microcolumn and determination by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS)

A selective matrix removal/separation/enrichment method, utilizing a microcolumn of a chelating resin with SH functional groups (Duolite GT-73), was proposed for the determination of Sb(III) in waters by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS). The resin was selective to Sb(III) at almost all pH and acidity values employed, whereas Sb(V) was not retained at all and could be determined after a pre-reduction step with l-cysteine. Spike recoveries were tested at various concentration levels in different water types and were found to vary between 85 and 118%. Accuracy of the proposed methodology was checked by analyzing a standard reference material and a good correlation was found between the determined (13.3 ± 1.1 μg l⁻¹) and the certified value (13.79 ± 0.42 μg l⁻¹). The method was applied to several bottled drinking water samples for antimony determination with and without preconcentration and none of the samples were found to contain antimony above the permissible level (5 μg l⁻¹). The characteristic concentration (the concentration of the analyte corresponding to an absorbance of 0.0044) was 0.55 μg l⁻¹ and the 3 s limit of detection (LOD) based on five times preconcentration was 0.06 μg l⁻¹. The applicability of the microcolumn separation/preconcentration/matrix removal method for flow injection systems was also demonstrated.     

DNA and PNA sensing on mercury and carbon electrodes by using methylene blue as an electrochemical label

Described here are the electrochemical parameters for MB on binding to DNA at hanging mercury drop electrode (HMDE), glassy carbon electrode (GCE), and carbon paste electrode (CPE) in the solution and at the electrode surface. MB, which interacts with the immobilized calf thymus DNA, was detected by using single-stranded DNA-modified HMDE or CPE (ssDNA-modified HMDE or CPE), bare HMDE or CPE, and double-stranded DNA-modified HMDE or CPE (dsDNA-modified HMDE or CPE) in combination with adsorptive transfer stripping voltammetry (AdTSV), differential pulse voltammetry (DPV), and alternating current voltammetry (ACV) techniques. The structural conformation of DNA and hybridization between synthetic peptide nucleic acid (PNA) and DNA oligonucleotides were determined by the changes in the voltammetric peak of MB. The PNA and DNA probes were also challenged with excessive and equal amount of noncomplementary DNA and a mixture that contained one-base mismatched and target DNA. The partition coefficient was also obtained from the signal of MB with probe, hybrid, and ssDNA-modified GCEs. The effect of probe, target, and ssDNA concentration upon the MB signal was investigated. These results demonstrated that MB could be used as an effective electroactive hybridization indicator for DNA biosensors. Performance characteristics of the sensor are described, along with future prospects.     

Influence of In Vitro Human Digestion Simulation on the Phenolics Contents and Biological Activities of the Aqueous Extracts from Turkish Cistus Species

Oxidative stress is one of the significant precursors of various metabolic diseases such as diabetes, Parkinson’s disease, cardiovascular diseases, cancer, etc. Various scientific reports have indicated that secondary plant metabolites play an important role in preventing oxidative stress and its harmful effects. In this respect, this study was planned to investigate the phenolic profile and antioxidant and antidiabetic potentials of the aqueous extracts from Turkish Cistus species by employing in vitro methods. In vitro digestion simulation procedure was applied to all extracts to estimate the bioavailability of their phenolic contents. Total phenolic, flavonoid, phenolic acid and proanthocyanidin contents were determined for all phases of digestion. In addition, changes in the quantity of the assigned marker flavonoids (tiliroside, hyperoside and quercitrin) were monitored by High-Performance Thin Layer Chromatography (HPTLC) analysis. The antioxidant activity potentials of the extracts were studied by various methods to reveal their detailed activity profiles. On the other hand, in vitro α-amylase and α-glucosidase enzymes and advanced-glycation end product (AGE) inhibitory activities of the extracts were determined to evaluate the antidiabetic potentials of extracts. The results showed that aqueous extracts obtained from the aerial parts of Turkish Cistus species have rich phenolic contents and potential antioxidant and antidiabetic activities; however, their bioactivity profiles and marker flavonoid concentrations might significantly be affected by human digestion. The results exhibited that total phenolic contents, antioxidant activities and diabetes-related enzyme inhibitions of the bioavailable samples were lower than non-digested samples in all extracts.     

Magnetic relaxation in a spin-1 Ising model near the second-order phase transition point

The magnetic relaxation of a spin-1 Ising model with bilinear and biquadratic interactions is formulated within the framework of statistical equilibrium theory and the thermodynamics of irreversible processes. Using a molecular-field expression for the magnetic Gibbs energy, the magnetic Gibbs energy produced in the irreversible process is calculated and time derivatives of the dipolar and quadrupolar order parameters are treated as fluxes conjugate to their appropriate generalized forces in the sense of Onsager theory. The kinetic equations are obtained by introducing kinetic coefficients that satisfy the Onsager relation. By solving these equations an expression is derived for the dynamic or complex magnetic susceptibility. From the real and imaginary parts of this expression, magnetic dispersion and absorption factor are calculated and analyzed near the second-order phase transition.