Cationic gemini surfactants as pseudostationary phases in micellar electrokinetic chromatography. Part I: Effect of head group

Two cationic gemini surfactants with pyrrolidinium or alkyl ammonium head groups with but-2-yne spacers, but with the same length hydrocarbon chain have been characterized with respect to their aggregation behaviors and separation power as pseudostationary phases (PSPs) for micellar electrokinetic chromatography (MEKC). They were compared with a commonly used PSP, sodium dodecylsulfate (SDS). The results suggest that the head groups of the surfactants have some effect on physicochemical properties such as critical micelle concentration (CMC), C₂₀, γ_CMC, partial specific volume, methylene selectivity and mobilities of the surfactants. CMC values of G1, G2 and SDS in pure water were found to be 0.82, 0.71, and 8.08 mM, respectively; they were reduced to 0.21, 0.11, and 3.0 mM when measured in 10 mM phosphate buffer at pH 7.0. G1 (α_CH2=2.74${\alpha }_{\text{C}{\text{H}}_2}=2.74$) and G2 (α_CH2=2.48${\alpha }_{\text{C}{\text{H}}_2}=2.48$) provided the most and the least hydrophobic environment, respectively. According to their partial specific volumes, geminis were found to have more flexible structures as compared with sodium dodecylsulfate. The effects of the head group structure were also characterized with the linear solvation energy relationship (LSER) model, which was able to evaluate the role of solute size, polarity/polarizability, and hydrogen bonding on retention and selectivity. The cohesiveness, hydrogen bond acidic and basic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention of the gemini surfactants. It should be noted that with their large positive coefficient a values, G1 and G2 were found to be stronger HB acceptors than anionic and most of the cationic surfactants studied in the literature.     

Complexation of metal ions with the novel diazadithia crown ether carrying two anthryl pendants in acetonitrile–tetrahydrofuran

A new crown ether carrying two anthryl groups with nitrogen–sulfur donor atom was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl anthracene. The influence of metal cations such as Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ on the spectroscopic properties of the ligand was investigated in acetonitrile–tetrahydofuran solution (1/1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Fe²⁺, Fe³⁺, Al³⁺, Cu²⁺ and Hg²⁺. The results of spectrophotometric titration experiments disclosed the complexation stoichiometry and complex stability constant of the novel ligand with Fe²⁺, Fe³⁺, Al³⁺, Cu²⁺and Hg²⁺cations. The presence of excess amounts of Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ cations caused an enhancement of anthryl fluorescence. The ligand showed good sensitivity for Zn²⁺ with respect to other metal cations with linear range and detection limit of 1.4 × 10^?7 to 4.1 × 10^?6 M and 1.0 × 10^?8 M respectively.     

Streptavidin Modified Carbon Nanotube Based Graphite Electrode for Label‐Free Sequence Specific DNA Detection

Disposable graphite pencil electrodes (PGE) modified with multiwalled carbon nanotubes (MWCNTs)‐streptavidin (STR) conjugates were used for electrochemical monitoring of label‐free DNA hybridization. The surface morphology of PGE electrode before and after hybridization was characterized by scanning electron microscopy. Electrochemical impedance spectroscopy was used to monitor each step of the construction of the DNA biosensor. The biosensor was demonstrated to have excellent selectivity, being able to differentiate complementary sequences from a noncomplementary ones and in addition select the target sequence of DNA from a mixture of other DNA without loss in current sensitivity.     

Annealing effects on structural, optical and electrical properties of e-beam evaporated CuIn0.5Ga0.5Te2 thin films

CuIn_0.5Ga_0.5Te₂ (CIGT) thin films have been prepared by e-beam evaporation from a single crystal powder synthesized by direct reaction of constituent elements in a stoichiometric proportion. Post-depositional annealing has been carried out at 300 and 350 °C. The compositions of the films were determined by energy dispersive X-ray analysis (EDXA) and it was found that there was a remarkable fluctuation in atomic percentage of the constituent elements following to the post-depositional annealing. X-ray diffraction analysis (XRD) has shown that as-grown films were amorphous in nature and turned into polycrystalline structure following to the annealing at 300 °C. The main peaks of CuIn_0.5Ga_0.5Te₂ and some minor peaks belonged to a binary phase Cu₂Te appeared after annealing at 300 °C, whereas for the films annealed at 350 °C single phase of the CuIn_0.5Ga_0.5Te₂ chalcopyrite structure was observed with the preferred orientation along the (1 1 2) plane. The effect of annealing on and near surface regions has been studied using X-ray photoelectron spectroscopy (XPS). The results indicated that there was a considerable variation in surface composition following to the annealing process. The transmission and reflection measurements have been carried out in the wavelength range of 200-1100 nm. The absorption coefficients of the films were found to be in the order of 10⁴ cm⁻¹ and optical band gaps were determined as 1.39, 1.43 and 1.47 eV for as-grown and films annealed at 300 and 350 °C, respectively. The temperature dependent conductivity and photoconductivity measurements have been performed in the temperature range of −73 to 157 °C and the room temperature resistivities were found to be around 3.4 × 10⁷ and 9.6 × 10⁶ (Ω cm) for the as-grown and annealed films at 350 °C, respectively.     

Numerical simulation of magnetohydrodynamic buoyancy-induced flow in a non-isothermally heated square enclosure

Numerical simulation of magnetohydrodynamic (MHD) buoyancy-induced heat transfer and fluid flow has been analyzed in a non-isothermally heated square enclosure using finite volume method. The bottom wall of enclosure were heated and cooled with a sinusoidal function and top wall was cooled isothermally. Vertical walls of the enclosure were adiabatic. Effects of Rayleigh number (Ra = 10⁴, 10⁵ and 10⁶), Hartman number (Ha = 0, 50 and 100) and amplitude of sinusoidal function (n = 0.25, 0.5 and 1) on temperature and flow fields were analyzed. It was observed that heat transfer was decreased with increasing Hartmann number and decreasing value of amplitude of sinusoidal function.     

Sobolev regularity for first order mean field games

In this paper we obtain Sobolev estimates for weak solutions of first order variational Mean Field Game systems with coupling terms that are local functions of the density variable. Under some coercivity conditions on the coupling, we obtain first order Sobolev estimates for the density variable, while under similar coercivity conditions on the Hamiltonian we obtain second order Sobolev estimates for the value function. These results are valid both for stationary and time-dependent problems. In the latter case the estimates are fully global in time, thus we resolve a question which was left open in [23]. Our methods apply to a large class of Hamiltonians and coupling functions.     

Bioconjugation of D‐glucuronic acid sodium salt to well‐defined primary amine‐containing homopolymers and block copolymers

The synthesis of well‐defined carboxylic acid‐functionalized glycopolymers prepared via one‐step postpolymerization modification of poly(N‐[3‐aminopropyl] methacrylamide) (PAPMA), a water‐soluble primary amine methacrylamide, in aqueous medium is demonstrated. PAPMA was first polymerized via aqueous reversible addition‐fragmentation chain transfer polymerization in aqueous buffer using 4‐cyanopentanoic acid dithiobenzoate as the chain transfer agent and 4,4′‐azobis(4‐cyanovaleric acid) (V‐501) as the initiator at 70 °C. The resulting well‐defined PAPMA was then conjugated with D ‐glucuronic acid sodium salt through reductive amination in alkaline medium (pH 8.5) at 45 °C. The successful bioconjugation was proven through proton (¹H) and carbon (¹³C) nuclear magnetic resonance spectroscopy and matrix‐assisted laser desorption/ionization time of flight mass spectrometry analysis, which indicated near quantitative conversion. A similar bioconjugation reaction was conducted with poly(2‐aminoethyl methacrylate) (PAEMA) and poly(2‐aminoethyl methacrylate‐b‐poly(N‐[2‐hydroxypropyl]methacrylamide) (PAEMA‐b‐PHPMA). For the PAEMA homopolymers and block copolymers, however, lower conversion was obtained, most likely because of degradation reactions of PAEMA in alkaline medium. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3052–3061, 2010     

Three dimensional architectures of ultra-high density semiconducting nanowires deposited on chip

We report a "clean" and fast process, utilizing supercritical carbon dioxide, for producing ultrahigh densities, up to 10(12) nanowires per square centimeter, of ordered germanium nanowires on silicon and quartz substrates. Uniform mesoporous thin films were employed as templates for the nucleation and growth of unidirectional nanowire arrays orientated almost perpendicular to a substrate surface. Additionally, these nanocomposite materials display room-temperature photoluminescence (PL), the energy of which is dependent on the diameter of the encased nanowires. The ability to synthesis ultrahigh-density arrays of semiconducting nanowires on-chip is a key step in future "bottom-up" fabrication of multilayered device architectures for nanoelectronic and optoelectronic devices.     

Synthesis and metal-ion binding properties of new N2S4- and N2S5-donor macrocycles

Synthetic procedures for new N₂S₄- and N₂S₅-donor macrocycles (2 and 4) were given. The ligands were prepared by the reaction of NaBH₄ with the appropriate macrocyclic diamide in the presence of boron trifluoride ethyl etherate in dry tetrahydrofuran (THF). Solvent extraction method was used to evaluate metal-ion binding properties of the new ligands. The solvent extraction experiments suggested that the reduced macrocycles have Ag⁺ and Hg²⁺ selectivities compared to Pb²⁺, Co²⁺, Zn²⁺, Ni²⁺, Cu²⁺, Mn²⁺ and Cd²⁺ ions. The extraction constants (log K _ex) and complex compositions were determined for Ag⁺ and Hg²⁺ complex of compound (4).     

2‐Meth­oxy‐4‐[(5‐oxo‐2‐phenyl‐4,5‐dihydro‐1,3‐oxazol‐4‐yl­idene)meth­yl]­phenyl 4‐methyl­benzene­sulfonate

Mol­ecules of the title compound, C₂₄H₁₉NO₆S, adopt the Z configuration and have a distorted tetra­hedral geometry around the S atom. The oxazolone, 2‐phenyl and methoxy­phenyl rings are approximately coplanar. The C atom between the methoxy­phenyl and oxazolone rings displays a distorted trigonal bonding geometry. Pairs of mol­ecules are linked into dimers through weak C—H⋯O hydrogen bonds.