Multicomponent kinetic spectrophotometric determination of pefloxacin and norfloxacin in pharmaceutical preparations and human plasma samples with the aid of chemometrics

A spectrophotometric method for the simultaneous determination of the important pharmaceuticals, pefloxacin and its structurally similar metabolite, norfloxacin, is described for the first time. The analysis is based on the monitoring of a kinetic spectrophotometric reaction of the two analytes with potassium permanganate as the oxidant. The measurement of the reaction process followed the absorbance decrease of potassium permanganate at 526 nm, and the accompanying increase of the product, potassium manganate, at 608 nm. It was essential to use multivariate calibrations to overcome severe spectral overlaps and similarities in reaction kinetics. Calibration curves for the individual analytes showed linear relationships over the concentration ranges of 1.0–11.5 mg L−1 at 526 and 608 nm for pefloxacin, and 0.15–1.8 mg L−1 at 526 and 608 nm for norfloxacin. Various multivariate calibration models were applied, at the two analytical wavelengths, for the simultaneous prediction of the two analytes including classical least squares (CLS), principal component regression (PCR), partial least squares (PLS), radial basis function-artificial neural network (RBF-ANN) and principal component-radial basis function-artificial neural network (PC-RBF-ANN). PLS and PC-RBF-ANN calibrations with the data collected at 526 nm, were the preferred methods—%RPET not, vert, similar 5, and LODs for pefloxacin and norfloxacin of 0.36 and 0.06 mg L−1, respectively. Then, the proposed method was applied successfully for the simultaneous determination of pefloxacin and norfloxacin present in pharmaceutical and human plasma samples. The results compared well with those from the alternative analysis by HPLC.

Predictions of angle dependent tortuosity and elasticity effects on sound propagation in cancellous bone

The anisotropic pore structure and elasticity of cancellous bone cause wave speeds and attenuation in cancellous bone to vary with angle. Previously published predictions of the variation in wave speed with angle are reviewed. Predictions that allow tortuosity to be angle dependent but assume isotropic elasticity compare well with available data on wave speeds at large angles but less well for small angles near the normal to the trabeculae. Claims for predictions that only include angle-dependence in elasticity are found to be misleading. Audio-frequency data obtained at audio-frequencies in air-filled bone replicas are used to derive an empirical expression for the angle-and porosity-dependence of tortuosity. Predictions that allow for either angle dependent tortuosity or angle dependent elasticity or both are compared with existing data for all angles and porosities.

Metal oxide nanofibres membranes assembled by spin-coating method

Ceramic membranes are of particular interest in many industrial processes due to their ability to function under extreme conditions while maintaining their chemical and thermal stability. Major structural deficiencies under conventional fabrication approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using larger titanate nanofibres and smaller boehmite nanofibres. This yields a radical change in membrane texture. The differences in the porous supports have no substantial influences on the texture of resulting membranes. The membranes with top layer of nanofibres coated on different porous supports by spin-coating method have similar size of the filtration pores, which is in a range of 10–100 nm. These membranes are able to effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. The retention can attain more than 95%, while maintaining a high flux rate about 900 L m-2 h. The calcination after spin-coating creates solid linkages between the fibres and between fibres and substrate, in addition to convert boehmite into -alumina nanofibres. This reveals a new direction in membrane fabrication.

New Approach on Robust Delay-Dependent H∞ Control for Uncertain T-S Fuzzy Systems With Interval Time-Varying Delay

This paper investigates the robust H∞ control for Takagi-Sugeno (T-S) fuzzy systems with interval time-varying delay. By employing a new and tighter integral inequality and constructing an appropriate type of Lyapunov functional, delay-dependent stability criteria are derived for the control problem. Because neither any model transformation nor free weighting matrices are employed in our theoretical derivation, the developed stability criteria significantly improve and simplify the existing stability conditions. Also, the maximum allowable upper delay bound and controller feedback gains can be obtained simultaneously from the developed approach by solving a constrained convex optimization problem. Numerical examples are given to demonstrate the effectiveness of the proposed methods.

Kinematics of intracellular chlamydiae provide evidence for contact-dependent development

A crucial process of chlamydial development involves differentiation of the replicative reticulate body (RB) into the infectious elementary body (EB). We present experimental evidence to provide support for a contact-dependent hypothesis for explaining the trigger involved in differentiation. We recorded live-imaging of Chlamydia trachomatis-infected McCoy cells at key times during development and tracked the temporospatial trajectories of individual chlamydial particles. We found that movement of the particles is related to development. Early to mid-developmental stages involved slight wobbling of RBs. The average speed of particles increased sharply at 24 h postinfection (after the estimated onset of RB to EB differentiation). We also investigated a penicillin-supplemented culture containing EBs, RBs, and aberrantly enlarged, stressed chlamydiae. Near-immobile enlarged particles are consistent with their continued tethering to the chlamydial inclusion membrane (CIM). We found a significantly negative, nonlinear association between speed and size/type of particles, providing further support for the hypothesis that particles become untethered near the onset of RB to EB differentiation. This study establishes the relationship between the motion properties of the chlamydiae and developmental stages, whereby wobbling RBs gradually lose contact with the CIM, and RB detachment from the CIM is coincidental with the onset of late differentiation.

Incidental walking activity is sufficient to induce time-dependent conditioning of the Achilles tendon

The Achilles tendon has been seen to exhibit time-dependent conditioning when isometric muscle actions were of a prolonged duration, compared to those involved in dynamic activities, such as walking. Since, the effect of short duration muscle activation associated with dynamic activities is yet to be established, the present study aimed to investigate the effect of incidental walking activity on Achilles tendon diametral strain. Eleven healthy male participants refrained from physical activity in excess of the walking required to carry out necessary daily tasks and wore an activity monitor during the 24 h study period. Achilles tendon diametral strain, 2 cm proximal to the calcaneal insertion, was determined from sagittal sonograms. Baseline sonographic examinations were conducted at ∼08:00 h followed by replicate examinations at 12 and 24 h. Walking activity was measured as either present (1) or absent (0) and a linear weighting function was applied to account for the proximity of walking activity to tendon examination time. Over the course of the day the median (min, max) Achilles tendon diametral strain was −11.4 (4.5, −25.4)%. A statistically significant relationship was evident between walking activity and diametral strain (P < 0.01) and this relationship improved when walking activity was temporally weighted (AIC 131 to 126). The results demonstrate that the short yet repetitive loads generated during activities of daily living, such as walking, are sufficient to induce appreciable time-dependant conditioning of the Achilles tendon. Implications arise for the in vivo measurement of Achilles tendon properties and the rehabilitation of tendinopathy.

A psychometric comparison of the Toronto Alexithymia Scale (TAS-20) and the Observer Alexithymia Scale (OAS) in an alcohol-dependent sample

Alexithymia is characterised by deficits in emotional insight and self reflection, that impact on the efficacy of psychological treatments. Given the high prevalence of alexithymia in Alcohol Use Disorders, valid assessment tools are critical. The majority of research on the relationship between alexithymia and alcohol-dependence has employed the self-administered Toronto Alexithymia Scale (TAS-20). The Observer Alexithymia Scale (OAS) has also been recommended. The aim of the present study was to assess the validity and reliability of the OAS and the TAS-20 in an alcohol-dependent sample. Two hundred and ten alcohol-dependent participants in an outpatient Cognitive Behavioral Treatment program were administered the TAS-20 at assessment and upon treatment completion at 12 weeks. Clinical psychologists provided observer assessment data for a subsample of 159 patients. The findings confirmed acceptable internal consistency, test-retest reliability and scale homogeneity for both the OAS and TAS-20, except for the low internal consistency of the TAS-20 EOT scale. The TAS-20 was more strongly associated with alcohol problems than the OAS.

The impact of spin on Australian real estate journalism : a Queensland study

Regardless of ‘bear’ or ‘bull’ markets, the great Australian dream remains to own your own home. Central to this dream of home ownership is unflagging interest in the property market, reflected in bulging real estate news sections of newspapers in South East Queensland, the focus area for this thesis research. While there has been much scholarly research into other areas of public relations spin and its impact on news-gathering processes, there appears to be next to no research on real estate spin, how it is prepared and by whom, and journalism’s attitude to and the managing of the spin. Real estate spin remains an under-researched topic requiring further investigation not only in South East Queensland but Australia-wide given the ‘big bucks’ allotted to the promotion of real estate and the income it generates for news media outlets, particularly newspapers. This thesis examines the influence of public relations practitioners and journalists specialising in real estate spin through interviews, content analysis, and how real estate spin envelopes itself in today’s society. From content analyses and observations of journalism in the real estate rounds of the two major newspapers in South East Queensland, I found that journalists were using massive quantities of real estate spin supplied by PR practitioners and other associated industry sources. This spin is supplanting investigative newsroom journalism, thus allowing newspapers to operate with minimal staffing levels yet still able to publish large weekly real estate news sections. My research also revealed growing commercialisation of real estate news through increasing outsourcing of journalistic work to a writing bureau, which could jeopardise both the professions of journalism and public relations in the future.

Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

The ultra-low friction of the articular surface is pH-dependent and is built on a hydrophobic underlay including a hypothesis on joint lubrication mechanism

In this study, the influence of pH on interfacial energy distributed over the phospholipids-bilayer surface model and the effect of hydrophobicity on coefficient of friction (f) were investigated by using microelectrophoresis. An important clinical implication of deficiency in hydrophobicity is the loss of phospholipids that is readily observed in osteoarthritis joints. This paper establishes the influence of pH on interfacial energy upon an increase f, which might be associated with a decrease of hydrophobicity of the articular surface.

Temperature and electric field dependent mobility in poly„3-hexylthiophene diodes

Current-voltage (I-V) curves of Poly(3-hexyl-thiophene) (P3HT) diodes have been collected to investigate the polymer hole-dominated charge transport. At room temperature and at low electric fields the I-V characteristic is purely Ohmic whereas at medium-high electric fields, experimental data shows that the hole transport is Trap Dominated - Space Charge Limited Current (TD-SCLC). In this regime, it is possible to extract the I-V characteristic of the P3HT/Al junction showing the ideal Schottky diode behaviour over five orders of magnitude. At high-applied electric fields, holes’ transport is found to be in the trap free SCLC regime. We have measured and modelled in this regime the holes’ mobility to evaluate its dependence from the electric field applied and the temperature of the device.

Scale-dependent fracture mode in Cu-Ni laminate composites

Fracture behavior of Cu-Ni laminate composites has been investigated by tensile testing. It was found that as the individual layer thickness decreases from 100 to 20nm, the resultant fracture angle of the Cu-Ni laminate changes from 72 degrees to 50 degrees. Cross-sectional observations reveal that the fracture of the Ni layers transforms from opening to shear mode as the layer thickness decreases while that of the Cu layers keeps shear mode. Competition mechanisms were proposed to understand the variation in fracture mode of the metallic laminate composites associated with length scale.