Desorption electrospray ionisation mass spectrometry reveals in situ modification of a hindered amine light stabiliser resulting from direct N–OR bond cleavage

Detection and characterisation of structural modifications of a hindered amine light stabiliser (HALS) directly from a polyester-based coil coating have been achieved by desorption electrospray ionisation mass spectrometry (DESI-MS) for the first time. In situ detection is made possible by exposing the coating to an acetone vapour atmosphere prior to analysis. This is a gentle and non-destructive treatment that allows diffusion of analyte to the surface without promoting lateral migration. Using this approach a major structural modification of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) was discovered where one N-ether piperidine moiety (N-OC8H17) is converted to a secondary piperidine (N–H). With the use of 2-dimensional DESI-MS imaging the modification was observed to arise during high curing temperatures (ca. 260 °C) and under simulated physiological conditions (80 °C, full solar spectrum). It is proposed that the secondary piperidine derivative is a result of a highly reactive aminyl radical intermediate produced by N–O homolytic bond cleavage. The nature of the bond cleavage is also suggested by ESR spin-trapping experiments employing α-phenyl-N-tert-butyl nitrone (PBN) in toluene at 80 °C. The presence of a secondary piperidine derivative in situ and the implication of N–OR competing with NO–R bond cleavage suggest an alternative pathway for generation of the nitroxyl radical—an essential requirement in anti-oxidant activity that has not previously been described for the N-ether sub-class of HALS.

Painting anatase (TiO2) nanocrystals on long nanofibers to prepare photocatalysts with large active surface for dye degradation and organic synthesis

Anatase TiO2 nanocrystals were painted on H-titanate nanofibers by using an aqueous solution of titanyl sulfate. The anatase nanocrystals were bonded solidly onto the titanate fibers through formation of coherent interfaces at which the oxygen atoms were shared by the nanocrystals and the fiber. This approach allowed us to create large anatase surfaces on the nanofibers, which are active in photocatalytic reactions. This method was also applied successfully to coat anatase nanocrystals on surfaces of fly ash and layered clay. The painted nanofibers exhibited a much higher catalytic activity for the photocatalytic degradation of sulforhodamine B and the selective oxidation of benzylamine to the corresponding imine (with a product selectivity >99%) under UV irradiation than both the parent H-titanate nanofibers and a commercial TiO2 powder, P25. We found that gold nanoparticles supported on H-titanate nanofibers showed no catalytic activity for the reduction of nitrobenzene to azoxybenzene, whereas the gold nanoparticles supported on the painted nanofibers and P25 could efficiently reduce nitrobenzene to azoxybenzene as the sole product under visible light irradiation. These results were different from those from the reduction on the gold nanoparticles photocatalyst on ZrO2, in which the azoxybenzene was the intermediate and converted to azobenzene quickly. Evidently, the support materials significantly affect the product selectivity of the nitrobenzene reduction. Finally, the new photocatalysts could be easily dispersed into and separated from a liquid because of their fibril morphology, which is an important advantage for practical applications.

Direct and quantitative detection of bacteriophage by “hearing” surface detachment using a quartz crystal microbalance

We show that it is possible to detect specifically adsorbed bacteriophage directly by breaking the interactions between proteins displayed on the phage coat and ligands immobilized on the surface of a quartz crystal microbalance (QCM). This is achieved through increasing the amplitude of oscillation of the QCM surface and sensitively detecting the acoustic emission produced when the bacteriophage detaches from the surface. There is no interference from nonspecifically adsorbed phage. The detection is quantitative over at least 5 orders of magnitude and is sensitive enough to detect as few as 20 phage. The method has potential as a sensitive and low-cost method for virus detection.

Manoeuvring control of underactuated surface vessels using manifold regulation for Port-Hamiltonian systems

This paper considers the manoeuvring of underactuated surface vessels. The control objective is to steer the vessel to reach a manifold which encloses a waypoint. A transformation of configuration variables and a potential field are used in a Port-Hamiltonian framework to design an energy-based controller. With the proposed controller, the geometric task associated with the manoeuvring problem depends on the desired potential energy (closed-loop) and the dynamic task depends on the total energy and damping. Therefore, guidance and motion control are addressed jointly, leading to model-energy-based trajectory generation.

A nonlinear observer for estimating transverse stability parameters of marine surface vessels

This paper presents a nonlinear observer for estimating parameters associated with the restoring term of a roll motion model of a marine vessel in longitudinal waves. Changes in restoring, also referred to as transverse stability, can be the result of changes in the vessel's centre of gravity due to, for example, water on deck and also in changes in the buoyancy triggered by variations in the water-plane area produced by longitudinal waves -- propagating along the fore-aft direction along the hull. These variations in the restoring can change dramatically the dynamics of the roll motion leading to dangerous resonance. Therefore, it is of interest to estimate and detect such changes.

Tragedy and assimilation: Occupying the patterned surface

This chapter draws on biographical data about two notable pattern designers of wall surfaces in the interior. Both had personal histories of multiple careers and geographical locations and both their lives ended in mysterious circumstances. One of the pattern designers, Jim Thompson, disappeared in the Malaysian highlands in 1967 and was never found. The other, Florence Broadhurst, was brutally murdered in 1977; her case remains unsolved. This chapter theorizes that the patterned surface attracted Broadhurst and Thompson as a space to occupy and record their divergent pasts, and questions what it is to lose oneself in the surface of the interior, to find freedom (or slavery) in the abdication of control. This notion is further evidenced in creative works, including the Australian film Candy and the work by skin illustrator Emma Hack. What is it to work with the self as a two-dimensional representation in the outside world? Occupying the surface suggests a reflexive relationship with identity, that makes-over and re-shapes truths, lies and re-constructions. The chapter reminds us that the surface is never in stasis.

Similarity solutions for flow and heat transfer of non-Newtonian fluid over a stretching surface

Similarity solutions are carried out for flow of power law non-Newtonian fluid film on unsteady stretching surface subjected to constant heat flux. Free convection heat transfer induces thermal boundary layer within a semi-infinite layer of Boussinesq fluid. The nonlinear coupled partial differential equations (PDE) governing the flow and the boundary conditions are converted to a system of ordinary differential equations (ODE) using two-parameter groups. This technique reduces the number of independent variables by two, and finally the obtained ordinary differential equations are solved numerically for the temperature and velocity using the shooting method. The thermal and velocity boundary layers are studied by the means of Prandtl number and non-Newtonian power index plotted in curves.

Surface dosimetry for very small X-ray beams

Introduction The dose to skin surface is an important factor for many radiotherapy treatment techniques. It is known that TPS predicted surface doses can be significantly different from actual ICRP skin doses as defined at 70 lm. A number of methods have been implemented for the accurate determination of surface dose including use of specific dosimeters such as TLDs and radiochromic film as well as Monte Carlo calculations. Stereotactic radiosurgery involves delivering very high doses per treatment fraction using small X-ray fields. To date, there has been limited data on surface doses for these very small field sizes. The purpose of this work is to evaluate surface doses by both measurements and Monte Carlo calculations for very small field sizes. Methods All measurements were performed on a Novalis Tx linear accelerator which has a 6 MV SRS X-ray beam mode which uses a specially thin flattening filter. Beam collimation was achieved by circular cones with apertures that gave field sizes ranging from 4 to 30 mm at the isocentre. The relative surface doses were measured using Gafchromic EBT3 film which has the active layer at a depth similar to the ICRP skin dose depth. Monte Carlo calculations were performed using the BEAMnrc/EGSnrc Monte Carlo codes (V4 r225). The specifications of the linear accelerator, including the collimator, were provided by the manufacturer. Optimisation of the incident X-ray beam was achieved by an iterative adjustment of the energy, spatial distribution and radial spread of the incident electron beam striking the target. The energy cutoff parameters were PCUT = 0.01 MeV and ECUT = 0.700 - MeV. Directional bremsstrahlung splitting was switched on for all BEAMnrc calculations. Relative surface doses were determined in a layer defined in a water phantom of the same thickness and depth as compared to the active later in the film. Results Measured surface doses using the EBT3 film varied between 13 and 16 % for the different cones with an uncertainty of 3 %. Monte Carlo calculated surface doses were in agreement to better than 2 % to the measured doses for all the treatment cones. Discussion and conclusions This work has shown the consistency of surface dose measurements using EBT3 film with Monte Carlo predicted values within the uncertainty of the measurements. As such, EBT3 film is recommended for in vivo surface dose measurements.

Monte Carlo simulations of small field output factors in solid phantoms

Introduction Total scatter factor (or output factor) in megavoltage photon dosimetry is a measure of relative dose relating a certain field size to a reference field size. The use of solid phantoms has been well established for output factor measurements, however to date these phantoms have not been tested with small fields. In this work, we evaluate the water equivalency of a number of solid phantoms for small field output factor measurements using the EGSnrc Monte Carlo code. Methods The following small square field sizes were simulated using BEAMnrc: 5, 6, 7, 8, 10 and 30 mm. Each simulated phantom geometry was created in DOSXYZnrc and consisted of a silicon diode (of length and width 1.5 mm and depth 0.5 mm) submersed in the phantom at a depth of 5 g/cm2. The source-to-detector distance was 100 cm for all simulations. The dose was scored in a single voxel at the location of the diode. Interaction probabilities and radiation transport parameters for each material were created using custom PEGS4 files. Results A comparison of the resultant output factors in the solid phantoms, compared to the same factors in a water phantom are shown in Fig. 1. The statistical uncertainty in each point was less than or equal to 0.4 %. The results in Fig. 1 show that the density of the phantoms affected the output factor results, with higher density materials (such as PMMA) resulting in higher output factors. Additionally, it was also calculated that scaling the depth for equivalent path length had negligible effect on the output factor results at these field sizes. Discussion and conclusions Electron stopping power and photon mass energy absorption change minimally with small field size [1]. Also, it can be seen from Fig. 1 that the difference from water decreases with increasing field size. Therefore, the most likely cause for the observed discrepancies in output factors is differing electron disequilibrium as a function of phantom density. When measuring small field output factors in a solid phantom, it is important that the density is very close to that of water.

Direct and quantitative detection of bacteriophage by "hearing" surface detachment using a quartz crystal microbalance

We show that it is possible to detect specifically adsorbed bacteriophage directly by breaking the interactions between proteins displayed on the phage coat and ligands immobilized on the surface of a quartz crystal microbalance (QCM). This is achieved through increasing the amplitude of oscillation of the QCM surface and sensitively detecting the acoustic emission produced when the bacteriophage detaches from the surface. There is no interference from nonspecifically adsorbed phage. The detection is quantitative over at least 5 orders of magnitude and is sensitive enough to detect as few as 20 phage. The method has potential as a sensitive and low-cost method for virus detection.

Probing the surface oxidation of chemically synthesised gold nanospheres and nanorods

In this study, the electrochemical behaviour of commercially available gold spheres and rods stabilised by carboxylic acid and cetyl trimethyl ammonium bromide (CTAB) moieties, respectively, are investigated. The cyclic voltammetric behaviour in acidic electrolyte is distinctly different with the nanorods exhibiting unusual oxidative behaviour due to an electrodissolution process. The nanospheres exhibited responses typical of a highly defective surface which significantly impacted on electrocatalytic activity. A repetitive potential cycling cleaning procedure was also investigated which did not improve the activity of the nanorods and resulted in deactivating the gold spheres due to decreasing the level of surface defects.

The invasive and metastatic properties of hormone-independent but hormone-responsive variants of MCF-7 human breast cancer cells

We have previously isolated a series of MCF-7 human breast cancer cell variants which no longer require estrogen-supplementation for tumor growth in nude mice (Clarke et al. Proc Natl Acad Sci USA 86: 3649-3653, 1989). We now report that these hormone-independent and hormone-responsive variants (MIII, MCF7/LCC1) can invade locally from solid mammary fat pad tumors, and produce primary extensions on the surface of intraperitoneal structures including liver, pancreas, and diaphragm. Both lymphatic and hematogenous dissemination are observed, resulting in the establishing of pulmonary, bone, and renal metastases. The pattern of metastasis by MIII and MCF7/LCC1 cells closely resembles that frequently observed in breast cancer patients, and provides the first evidence of metastasis from MCF-7 cells growing in vivo without supplementary estrogen. The interexperimental incidence of metastases, and the time from cell inoculation to the appearance of metastatic disease are variable. The increased metastatic potential is not associated with an increase in either the level of laminin attachment, laminin receptor mRNA expression, or secreted type IV collagenolytic activity. We also did not detect a significant decrease in the steady-state mRNA levels of the metastasis inhibitor nm23 gene. However, when growing without estrogen in vitro, MCF7/LCC1 cells produce elevated levels of the estrogen-inducible cathepsin D enzyme.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Epithelial-mesenchymal interconversions in normal ovarian surface epithelium and ovarian carcinomas : an exception to the norm

Cancer that arises from the ovarian surface epithelium (OSE) accounts for approximately 90% of human ovarian cancer, and is the fourth leading cause of cancer-related deaths among women in developed countries. The pathophysiology of epithelial ovarian cancer is still unclear because of the poor understanding of the complex nature of its development and the unusual mechanism(s) of disease progression. Recent studies have reported epithelial-mesenchymal transition (EMT) in cultured OSE and ovarian cancer cell lines in response to various stimuli, but our understanding of the importance of these observations for normal ovarian physiology and cancer progression is not well established. This review highlights the current literature on EMT-associated events in normal OSE and ovarian cancer cell lines, and discusses its implication for normal ovarian function as well as acquisition of neoplastic phenotypes. The pathological changes in OSE in response to EMT during neoplastic transformation and the contribution of hormones, growth factors, and cytokines that initiate and drive EMT to sustain normal ovarian function, as well as cancer development and progression are also discussed. Finally, emphasis is placed on the clinical implications of EMT and potential therapeutic opportunities that may arise from these observations have been proposed.

A novel identification method for ultra trace detection of biomolecules using functionalised Surface Enhanced Raman Spectroscopy (SERS)

This thesis developed a new method for measuring extremely low amounts of organic and biological molecules, using Surface enhanced Raman Spectroscopy. This method has many potential applications, e.g. medical diagnosis, public health, food provenance, antidoping, forensics and homeland security. The method development used caffeine as the small molecule example, and erythropoietin (EPO) as the large molecule. This method is much more sensitive and specific than currently used methods; rapid, simple and cost effective. The method can be used to detect target molecules in beverages and biological fluids without the usual preparation steps.