Polyfluorene Thin Films Synthesized by a Novel Plasma Polymerization Method

The synthesis of polyfluorene (PF) thin films by simultaneously superposing a continuous and pulsed discharge and the characterizations of these samples are presented. The double discharge plasma system is constructed by superposing two discharges; namely, a low pressure dc glow one and a high current pulsed one. The fluorene monomer in powder form was vaporized in the system at argon plasma without any modification, at 0.5 mbar operating pressure. The structure of the thin films was investigated via XPS, UV–visible, FTIR, XRD and SEM. The FTIR and the UV–visible results revealed that the fluorene structure was retained at the produced samples. Semi-conducting behavior was established, and upon the iodine doping, the optical energy band gap (E _g ) dropped down from 3.7 to 2.4 eV. The morphology of the synthesized PF thin films was amorphous, with granular structures of different sizes depending on the location of the substrate.     

Development and validation of an LC‐MS/MS method for simultaneous quantitative analysis of free and conjugated bisphenol A in human urine

Bisphenol A (BPA) is an environmental endocrine‐disrupting chemicals that is widely used in common consumer products. There is an increasing concern regarding human exposure to BPA owing to the potential adverse effects associated with its estrogenic activity. For assessing environmental exposure to BPA, it is essential to have a sensitive, accurate and selective analytical method, especially one that can detect low BPA levels in complex sample matrices. In this study, we developed and validated an accurate, sensitive, and robust liquid chromatography–tandem mass spectrometry method for simultaneous quantification of free BPA and BPA β‐d ‐glucuronide (BPA‐gluc) concentrations in human urine with only a single injection. Calibration curves were linear over a concentration range of 1–100 ng/mL for BPA and 10–1000 ng/mL for BPA‐gluc. The levels of the analytes were determined quantitatively with HPLC/ESI‐MS/MS by using negative electrospray ionization in the select ion monitoring mode and a pentaflouraphenyl propyl column. The validated method was applied to the analysis of spot urine specimens collected from randomly selected healthy human subjects. Copyright © 2013 John Wiley & Sons, Ltd.     

Low Reynolds number aerodynamics of free-to-roll low aspect ratio wings

The aerodynamics of thin, flat-plate wings of various planforms (rectangular, elliptical and Zimmerman) have been studied in free-to-roll experiments in a wind tunnel. Non-zero trim angles at low angles of attack, self-induced roll oscillations with increasing angle of attack and even autorotation in some cases were observed. The rectangular wings with round leading-edge had non-zero trim angles at low incidences due to the asymmetric development of the three-dimensional separation bubble at these low Reynolds numbers. With increasing angle of attack, the bubble increases in length and once reattachment is lost, large amplitude roll oscillations develop. The Strouhal number of the roll oscillations is of the order of 10⁻², which is in the same range as those expected for small aircraft experiencing atmospheric gusts. Velocity measurements revealed that variations in the strength of the vortices drove the rolling motion. At the mean roll angle, because of the time lag in the strength of the vortices, an asymmetric flow is generated, which results in a net rolling moment in the direction of the rolling motion.     

Thermal Decomposition Kinetics of Some Metal Complexes of 2,3-Hydroxyimino-4-phenyl-6-phenyazo-1-thia-4,5-diazacyclohexa-5-diene

The Ni(II), Cu(II) Co(II) and Zn(II) complexes of 2,3‐hydroxyimino‐4‐phenyl‐6‐phenyazo‐1‐thia‐4,5‐diaza‐ cyclohexa‐5‐diene (H₂L) were synthesized. Thermal behavior of these complexes was studied in dynamic nitrogen atmosphere by TA (thermogravimetric analysis), DTA (differential thermal analysis) and DTG (differential thermal gravimetry) techniques. The reaction order, the activation energies, the entropies, the enthalpies, the free energies, and the pre‐exponential factors of the thermal decomposition reactions were calculated from the thermogravimetric curves. The kinetic analysis of the thermogravimetric data was performed by using several methods such as MacCallum‐Tanner (MT), van Krevelen (vK), Madhusudanan‐Krishnan‐Ninan (MKN), Wanjun‐Yuwen‐Hen‐Cunxin (WYHC), Horowitz‐Metzger (HM) and Coats‐Redfern method (CR) based on the single heating rate. Most appropriate methods were determined for each decomposition step according to the least‐square linear regression. The Ni(II), Cu(II) Co(II) and Zn(II) complexes displayed one‐ or two‐stage decomposition pattern when heating in a dynamic nitrogen atmosphere and metal oxides remained as end products of the complexes. The characterization of the end products of the decomposition was performed by X‐ray diffraction.     

Vortex breakdown over a delta wing with oscillating leading edge flaps

 The effects of oscillating leading-edge flaps on leading-edge vortices and vortex breakdown were investigated for a delta wing with upward-deflected flaps. The variation of breakdown location revealed hysteresis loops. The time-averaged breakdown location over one cycle may move upstream or downstream compared to the quasi-steady case, depending on the amplitude of flap oscillations and angle of attack. Measurements of the phase-averaged velocity upstream of breakdown did not reveal any correlation to the response of breakdown location. The effect of oscillating flaps is largest when the breakdown location is near the trailing-edge region in the static case. Received: 2 February 1997/Accepted: 7 April 1997     

Effect of Operating Conditions in Production of Diagnostic Salmonella Enteritidis O-Antigen-Specific Monoclonal Antibody in Different Bioreactor Systems

In this study, different cultivation systems such as roller bottles (RB), 5-L stirred-tank bioreactor (STR), and disposable bioreactors were used to cultivate hybridoma for lab-scale production of Salmonella Enteritidis O-antigen-specific monoclonal antibody (MAb). Hybridoma cell line was cultivated in either serum-containing or serum-free medium (SFM) culture conditions. In STR, MAb production scaled up to 4 L, and production capabilities of the cells were also evaluated in different featured production systems. Moreover, the growth parameters of the cells in all production systems such as glucose consumption, lactate and ammonia production, and also MAb productivities were determined. Collected supernatants from the reactors were concentrated by a cross-flow filtration system. In conclusion, cells were not adapted to SFM in RB and STR. Therefore, less MAb titer in both STR and RB systems with SFM was observed compared to the cultures containing fetal bovine serum-supplemented medium. A higher MAb titer was gained in the membrane-aerated system compared to those in STR and RB. Although the highest MAb titer was obtained in the static membrane bioreactor system, the highest productivity was obtained in STR operated in semicontinuous mode with overlay aeration.     

In Vitro Inhibition Effect of Some Dihydroxy Coumarin Compounds on Purified Human Serum Paraoxonase 1 (PON1)

Human serum paraoxonase 1 (PON1; EC 3.1.8.1) is a high-density lipoprotein associated, calcium-dependent enzyme that hydrolyses aromatic esters, organophosphates and lactones and can protect the low-density lipoprotein against oxidation. In this study, in vitro inhibition effect of some dihydroxy coumarin compounds namely 6,7-dihydroxy-3-(2-methylphenyl)-2H-chromen-2-one (A), 6,7-dihydroxy-3-(3-methylphenyl)-2H-chromen-2-one (B) and 6,7-dihydroxy-3-(4-methylphenyl)-2H-chromen-2-one (C) on purified PON1 were investigated by using paraoxon as a substrate. PON1 was purified using two-step procedures, namely ammonium sulphate precipitation and Sepharose-4B-l-tyrosine-1-naphthylamine hydrophobic interaction chromatography. The purified enzyme had a specific activity of 11.76?U/mg. The dihydroxy coumarin derivatives of A and B compounds inhibited PON1 enzyme activity in a noncompetitive inhibition manner with K _i of 0.0080?±?0.256 and 0.0003?±?0.018?mM values, respectively. C compound exerted an uncompetitive inhibition of PON1 enzyme activity with K _i of 0.0010?±?0.173?mM. Moreover, dihydroxy coumarin derivatives of A, B and C compounds were effective inhibitors on purified human serum PON1 activity with IC₅₀ of 0.012, 0.022 and 0.003?mM values, respectively. IC₅₀ value of unsubstituted 6,7 dihydroxy coumarin was found as 0.178?mM. The present study has demonstrated that PON1 activity is very highly sensitive to studied coumarin derivatives.     

Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-<Emphasis Type="BoldItalic">tris</Emphasis>(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine and 2,4,6-<Emphasis Type="BoldItalic">tris</Emphasis>(4-carboxyphenylimino-4′-formylphenoxy)-1,3,5-triazine

Four new trinuclear Fe(III) complexes involving tetradenta Schiff bases N,N ¹ -bis(salicylidene) ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(salophH₂) with 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine (DCPI-TRIPOD) or 2,4,6-tris(4-carboxyphenylimino-4′-formylphenoxy)-1,3,5-triazine (CPI-TRIPOD) have been synthesized and characterized by means of elemental analysis carrying out ¹H-n.m.r., i.r. spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized as high-spin distorted octahedral Fe^III bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange.     

Effect of pre-strain and excess length on unsteady fluid–structure interactions of membrane airfoils

Aerodynamic characteristics of two-dimensional membrane airfoils were experimentally investigated in a wind tunnel. The effects of the membrane pre-strain and excess length on the unsteady aspects of the fluid–structure interaction were studied. The deformation of the membrane as a function of angle of attack and free-stream velocity was measured using a high-speed camera. These measurements were complemented by the measurements of unsteady velocity field with a high frame-rate Particle Image Velocimetry (PIV) system as well as smoke visualization. Membrane airfoils with excess length exhibit higher vibration modes, earlier roll-up of vortices, and smaller separated flow regions, whereas the membranes with pre-strain generally behave more similarly to a rigid airfoil. Measured frequencies of the membrane vibrations suggest a possible coupling with the wake instabilities at high incidences for all airfoils.