Automated surface sampling of lipids from worn contact lenses coupled with tandem mass spectrometry

The deposition of biological material (biofouling) onto polymeric contact lenses is thought to be a major contributor to lens discomfort and hence discontinuation of wear. We describe a method to characterize lipid deposits directly from worn contact lenses utilizing liquid extraction surface analysis coupled to tandem mass spectrometry (LESA-MS/MS). This technique effected facile and reproducible extraction of lipids from the contact lens surfaces and identified lipid molecular species representing all major classes present in human tear film. Our data show that LESA-MS/MS is a rapid and comprehensive technique for the characterization of lipid-related biofouling on polymer surfaces.

Surface analysis of lipids by mass spectrometry : More than just imaging

Mass spectrometry is now an indispensable tool for lipid analysis and is arguably the driving force in the renaissance of lipid research. In its various forms, mass spectrometry is uniquely capable of resolving the extensive compositional and structural diversity of lipids in biological systems. Furthermore, it provides the ability to accurately quantify molecular-level changes in lipid populations associated with changes in metabolism and environment; bringing lipid science to the "omics" age. The recent explosion of mass spectrometry-based surface analysis techniques is fuelling further expansion of the lipidomics field. This is evidenced by the numerous papers published on the subject of mass spectrometric imaging of lipids in recent years. While imaging mass spectrometry provides new and exciting possibilities, it is but one of the many opportunities direct surface analysis offers the lipid researcher. In this review we describe the current state-of-the-art in the direct surface analysis of lipids with a focus on tissue sections, intact cells and thin-layer chromatography substrates. The suitability of these different approaches towards analysis of the major lipid classes along with their current and potential applications in the field of lipid analysis are evaluated. © 2013 Elsevier Ltd. All rights reserved.

Ultraviolet Photodissociation of the N-Methylpyridinium Ion: Action Spectroscopy and Product Characterization

The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

Characterising in situ activation and degradation of hindered amine light stabilisers using liquid extraction surface analysis-mass spectrometry

Changes in the molecular structure of polymer antioxidants such as hindered amine light stabilisers (HALS) is central to their efficacy in retarding polymer degradation and therefore requires careful monitoring during their in-service lifetime. The HALS, bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TIN123) and bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TIN292), were formulated in different polymer systems and then exposed to various curing and ageing treatments to simulate in-service use. Samples of these coatings were then analysed directly using liquid extraction surface analysis (LESA) coupled with a triple quadrupole mass spectrometer. Analysis of TIN123 formulated in a cross-linked polyester revealed that the polymer matrix protected TIN123 from undergoing extensive thermal degradation that would normally occur at 292 degrees C, specifically, changes at the 1- and 4-positions of the piperidine groups. The effect of thermal versus photo-oxidative degradation was also compared for TIN292 formulated in polyacrylate films by monitoring the in situ conversion of N-CH3 substituted piperidines to N-H. The analysis confirmed that UV light was required for the conversion of N-CH3 moieties to N-H - a major pathway in the antioxidant protection of polymers - whereas this conversion was not observed with thermal degradation. The use of tandem mass spectrometric techniques, including precursor-ion scanning, is shown to be highly sensitive and specific for detecting molecular-level changes in HALS compounds and, when coupled with LESA, able to monitor these changes in situ with speed and reproducibility. (C) 2013 Elsevier B. V. All rights reserved.

A comparison of surface doses for very small field size x-ray beams : Monte Carlo calculations and radiochromic film measurements

Stereotactic radiosurgery treatments involve the delivery of very high doses for a small number of fractions. To date, there is limited data in terms of the skin dose for the very small field sizes used in these treatments. In this work, we determine relative surface doses for small size circular collimators as used in stereotactic radiosurgery treatments. Monte Carlo calculations were performed using the BEAMnrc code with a model of the Novalis 15 Trilogy linear accelerator and the BrainLab circular collimators. The surface doses were calculated at the ICRU skin dose depth of 70 m all using the 6 MV SRS x-ray beam. The calculated surface doses varied between 15 – 12% with decreasing values as the field size increased from 4 to 30 mm. In comparison, surface doses were measured using Gafchromic EBT3 film positioned at the surface of a Virtual Water phantom. The absolute agreement between calculated and measured surface doses was better than 2.5% which is well within the 20 uncertainties of the Monte Carlo calculations and the film measurements. Based on these results, we have shown that the Gafchromic EBT3 film is suitable for surface dose estimates in very small size fields as used in SRS.

Surface functionalization on the thermal conductivity of graphene–polymer nanocomposites

Exploring thermal transport in graphene-polymer nanocomposite is significant to its applications with better thermal properties. Interfacial thermal conductance between graphene and polymer matrix plays a critical role in the improvement of thermal conductivity of graphene-polymer nanocomposite. Unfortunately, it is still challenging to understand the interfacial thermal transport between graphene nanofiller and polymer matrix at small material length scale. To this end, using non-equilibrium molecular dynamics simulations, we investigate the interfacial thermal conductance of graphene-polyethylene (PE) nanocomposite. The influence of functionalization with hydrocarbon chains on the interfacial thermal conductance of graphene-polymer nanocomposites was studied, taking into account of the effects of model size and thermal conductivity of graphene. An analytical model is also used to calculate the thermal conductivity of nanocomposite. The results are considered to contribute to development of new graphene-polymer nanocomposites with tailored thermal properties.

Atomistic simulation of surface functionalization on the interfacial properties of graphene-polymer nanocomposites

Graphene has been increasingly used as nano sized fillers to create a broad range of nanocomposites with exceptional properties. The interfaces between fillers and matrix play a critical role in dictating the overall performance of a composite. However, the load transfer mechanism along graphene-polymer interface has not been well understood. In this study, we conducted molecular dynamics simulations to investigate the influence of surface functionalization and layer length on the interfacial load transfer in graphene polymer nanocomposites. The simulation results show that oxygen-functionalized graphene leads to larger interfacial shear force than hydrogen-functionalized and pristine ones during pull-out process. The increase of oxygen coverage and layer length enhances interfacial shear force. Further increase of oxygen coverage to about 7% leads to a saturated interfacial shear force. A model was also established to demonstrate that the mechanism of interfacial load transfer consists of two contributing parts, including the formation of new surface and relative sliding along the interface. These results are believed to be useful in development of new graphene-based nanocomposites with better interfacial properties.

Air navigation services in Australia and the United States : a comparative case study

The central document governing the global organization of Air Navigation Services (ANS) is the Convention on International Civil Aviation, commonly referred to as the “Chicago Convention,” whose original version was signed in that city in 1944. In the Convention, Contracting States agreed to ensure the minimum standards of ANS established by ICAO, a specialized United Nations agency created by the Convention. Emanating from obligations under the Chicago Convention, ANS has traditionally provided by departments of national governments. However, there is a widespread trend toward transferring delivery of ANS services outside of line departments of national governments to independent agencies or corporations. The Civil Air Navigation Services Organisation (CANSO), which is the trade association for independent ANS providers, currently counts approximately 60 members, and is steadily growing. However, whatever delivery mechanisms are chosen, national governments remain ultimately responsible for ensuring that adequate ANS services are available. The provision by governments of ANS reflects the responsibility of the state for safety, international relations, and indirectly, the macroeconomic benefits of ensuring a sound infrastructure for aviation. ANS is a “public good” and an “essential good” provided to all aircraft using a country’s airfields and airspace. However, ANS also represents a service that directly benefits only a limited number of users, notably aircraft owners and operators. The idea that the users of the system, rather than the taxpaying public, should incur the costs associated with ANS provision is inherent in the commercialization process. However, ICAO sets out broad principles for the establishment of user charges, which member states are expected to comply with. ICAO states that only distance flown and aircraft weights are acceptable parameters for use in a charging system. These two factors are considered to be easy to measure, bear a reasonable relationship to the value of service received, and do not discriminate due to factors such as where the flight originated or the nation of aircraft registration.

Binding of small mono- and oligomeric integrin ligands to membrane-embedded integrins monitored by surface plasmon-enhanced fluorescence spectroscopy

We recently developed a binding assay format by incorporating native transmembrane receptors into artificial phospholipid bilayers on biosensor devices for surface plasmon resonance spectroscopy. By extending the method to surface plasmon-enhanced fluorescence spectroscopy (SPFS), sensitive recording of the association of even very small ligands is enabled. Herewith, we monitored binding of synthetic mono- and oligomeric RGD-based peptides and peptidomimetics to integrins alphavbeta3 and alphavbeta5, after having confirmed correct orientation and functionality of membrane-embedded integrins. We evaluated integrin binding of RGD multimers linked together via aminohexanoic acid (Ahx) spacers and showed that the dimer revealed higher binding activity than the tetramer, followed by the RGD monomers. The peptidomimetic was also found to be highly active with a slightly higher selectivity toward alphavbeta3. The different compounds were also evaluated in in vitro cell adhesion tests for their capacity to interfere with alphavbeta3-mediated cell attachment to vitronectin. We hereby demonstrated that the different RGD monomers were similarly effective; the RGD dimer and tetramer showed comparable IC50 values, which were, however, significantly higher than those of the monomers. Best cell detachment from vitronectin was achieved by the peptidomimetic. The novel SPFS-binding assay platform proves to be a suitable, reliable, and sensitive method to monitor the binding capacity of small ligands to native transmembrane receptors, here demonstrated for integrins.

An intuitive multi-touch surface and gesture based interaction for video surveillance systems

This paper discusses the idea and demonstrates an early prototype of a novel method of interacting with security surveillance footage using natural user interfaces in place of traditional mouse and keyboard interaction. Current surveillance monitoring stations and systems provide the user with a vast array of video feeds from multiple locations on a video wall, relying on the user’s ability to distinguish locations of the live feeds from experience or list based key-value pair of location and camera IDs. During an incident, this current method of interaction may cause the user to spend increased amounts time obtaining situational and location awareness, which is counter-productive. The system proposed in this paper demonstrates how a multi-touch screen and natural interaction can enable the surveillance monitoring station users to quickly identify the location of a security camera and efficiently respond to an incident.

PCCP does exist

Neutral and cationic \[C-2,P-2] were investigated by a combination of mass spectrometry and electronic structure calculations. The cationic \[C-2,P-2](.+) potential energy surface including all relevant minima, transition states and fragmentation products was calculated at the B3LYP/6-311G(3df) level of theory. The most stable structures are linear PCCP.+ 1(.+) (E-rel=0 kcal mol(-1)), a three-membered ring with exocyclic phosphorus c-(PCC)-P 2(.+) (E-rel = 40.8 kcal mol(-1)), and the rhombic isomer 3(.+) (E-rel = 24.9 kcal mol(-1)). All fragmentation channels are significantly higher in energy than any of the \[C-2,P-2](.+) isomers. Experimentally, \[C-2,P-2](.+) ions are generated under high vacuum conditions by electron ionization of two different precursors. The fragmentation of \[C-2,P-2](.+) on collisional activation is preceded by rearrangement reactions which obscure the structural connectivity of the ions. The existence and the high stability of neutral \[C-2,P-2] were proved by a neutralization-reionization (NR) experiment. Although an unambiguous structural assignment of the neutral species cannot be drawn, both theory and experiment suggest that the long-sought neutral, linear PCCP 1 is generated using the NR technique.

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry

RATIONALE: Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. METHODS: Detection of the HALS TINUVINW123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAPW 5500 mass spectrometer. The detection of TINUVINW123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. RESULTS: Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer ' blooming'. CONCLUSIONS: For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright (C) 2012 John Wiley & Sons, Ltd.

Parental perceptions of the learner driver log book system in two Australian states

Objective While many jurisdictions internationally now require learner drivers to complete a specified number of hours of supervised driving practice before being able to drive unaccompanied, very few require learner drivers to complete a log book to record this practice and then present it to the licensing authority. Learner drivers in most Australian jurisdictions must complete a log book that records their practice thereby confirming to the licensing authority that they have met the mandated hours of practice requirement. These log books facilitate the management and enforcement of minimum supervised hours of driving requirements. Method Parents of learner drivers in two Australian states, Queensland and New South Wales, completed an online survey assessing a range of factors, including their perceptions of the accuracy of their child’s learner log book and the effectiveness of the log book system. Results The study indicates that the large majority of parents believe that their child’s learner log book is accurate. However, they generally report that the log book system is only moderately effective as a system to measure the number of hours of supervised practice a learner driver has completed. Conclusions The results of this study suggest the presence of a paradox with many parents possibly believing that others are not as diligent in the use of log books as they are or that the system is too open to misuse. Given that many parents report that their child’s log book is accurate, this study has important implications for the development and ongoing monitoring of hours of practice requirements in graduated driver licensing systems.

Use of simple pharmacokinetic modeling to characterize exposure of Australians to perfluorooctanoic acid and perfluorooctane sulfonic acid

Perflurooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) have been used for a variety of applications including fluoropolymer processing, fire-fighting foams and surface treatments since the 1950s. Both PFOS and PFOA are polyfluoroalkyl chemicals (PFCs), man-made compounds that are persistent in the environment and humans; some PFCs have shown adverse effects in laboratory animals. Here we describe the application of a simple one compartment pharmacokinetic model to estimate total intakes of PFOA and PFOS for the general population of urban areas on the east coast of Australia. Key parameters for this model include the elimination rate constants and the volume of distribution within the body. A volume of distribution was calibrated for PFOA to a value of 170ml/kgbw using data from two communities in the United States where the residents' serum concentrations could be assumed to result primarily from a known and characterized source, drinking water contaminated with PFOA by a single fluoropolymer manufacturing facility. For PFOS, a value of 230ml/kgbw was used, based on adjustment of the PFOA value. Applying measured Australian serum data to the model gave mean+/-standard deviation intake estimates of PFOA of 1.6+/-0.3ng/kgbw/day for males and females >12years of age combined based on samples collected in 2002-2003 and 1.3+/-0.2ng/kg bw/day based on samples collected in 2006-2007. Mean intakes of PFOS were 2.7+/-0.5ng/kgbw/day for males and females >12years of age combined based on samples collected in 2002-2003, and 2.4+/-0.5ng/kgbw/day for the 2006-2007 samples. ANOVA analysis was run for PFOA intake and demonstrated significant differences by age group (p=0.03), sex (p=0.001) and date of collection (p<0.001). Estimated intake rates were highest in those aged >60years, higher in males compared to females, and higher in 2002-2003 compared to 2006-2007. The same results were seen for PFOS intake with significant differences by age group (p<0.001), sex (p=0.001) and date of collection (p=0.016).

Influence of tilt and surface roughness on the outflow wind field of an impinging jet

A physical and numerical steady flow impinging jet has been used to simulate the bulk characteristics of a downburst-like wind field. The influence of downdraft tilt and surface roughness on the ensuing wall jet flow has been investigated. It was found that a simulated downdraft impinging the surface at a non-normal angle has the potential for causing larger structural loads than the normal impingement case. It was also found that for the current impinging jet simulations, surface roughness played a minor role in determining the storm maximum wind structure, but this influence increased as the wall jet diverged. However, through comparison with previous research it was found that the influence of surface roughness is Reynolds number dependent and therefore may differ from that reported herein for full-scale downburst cases. Using the current experimental results an empirical model has been developed for laboratory-scale impinging jet velocity structure that includes the influence of both jet tilt and surface roughness.