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.

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.

The use of acoustic indices to determine avian species richness in audio-recordings of the environment

Interpreting acoustic recordings of the natural environment is an increasingly important technique for ecologists wishing to monitor terrestrial ecosystems. Technological advances make it possible to accumulate many more recordings than can be listened to or interpreted, thereby necessitating automated assistance to identify elements in the soundscape. In this paper we examine the problem of estimating avian species richness by sampling from very long acoustic recordings. We work with data recorded under natural conditions and with all the attendant problems of undefined and unconstrained acoustic content (such as wind, rain, traffic, etc.) which can mask content of interest (in our case, bird calls). We describe 14 acoustic indices calculated at one minute resolution for the duration of a 24 hour recording. An acoustic index is a statistic that summarizes some aspect of the structure and distribution of acoustic energy and information in a recording. Some of the indices we calculate are standard (e.g. signal-to-noise ratio), some have been reported useful for the detection of bioacoustic activity (e.g. temporal and spectral entropies) and some are directed to avian sources (spectral persistence of whistles). We rank the one minute segments of a 24 hour recording in descending order according to an "acoustic richness" score which is derived from a single index or a weighted combination of two or more. We describe combinations of indices which lead to more efficient estimates of species richness than random sampling from the same recording, where efficiency is defined as total species identified for given listening effort. Using random sampling, we achieve a 53% increase in species recognized over traditional field surveys and an increase of 87% using combinations of indices to direct the sampling. We also demonstrate how combinations of the same indices can be used to detect long duration acoustic events (such as heavy rain and cicada chorus) and to construct long duration (24 h) spectrograms.

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

Direct writing of chitosan scaffolds using a robotic system

Purpose – This paper aims to present a novel rapid prototyping (RP) fabrication methods and preliminary characterization for chitosan scaffolds. Design – A desktop rapid prototyping robot dispensing (RPBOD) system has been developed to fabricate scaffolds for tissue engineering (TE) applications. The system is a computer-controlled four-axis machine with a multiple-dispenser head. Neutralization of the acetic acid by the sodium hydroxide results in a precipitate to form a gel-like chitosan strand. The scaffold properties were characterized by scanning electron microscopy, porosity calculation and compression test. An example of fabrication of a freeform hydrogel scaffold is demonstrated. The required geometric data for the freeform scaffold were obtained from CT-scan images and the dispensing path control data were converted form its volume model. The applications of the scaffolds are discussed based on its potential for TE. Findings – It is shown that the RPBOD system can be interfaced with imaging techniques and computational modeling to produce scaffolds which can be customized in overall size and shape allowing tissue-engineered grafts to be tailored to specific applications or even for individual patients. Research limitations/implications – Important challenges for further research are the incorporation of growth factors, as well as cell seeding into the 3D dispensing plotting materials. Improvements regarding the mechanical properties of the scaffolds are also necessary. Originality/value – One of the important aspects of TE is the design scaffolds. For customized TE, it is essential to be able to fabricate 3D scaffolds of various geometric shapes, in order to repair tissue defects. RP or solid free-form fabrication techniques hold great promise for designing 3D customized scaffolds; yet traditional cell-seeding techniques may not provide enough cell mass for larger constructs. This paper presents a novel attempt to fabricate 3D scaffolds, using hydrogels which in the future can be combined with cells.

The work of nurse practitioners : a national work sampling study

Aim: This paper is a report of a study of variations in the pattern of nurse practitioner work in a range of service fields and geographical locations, across direct patient care, indirect patient care and service-related activities. Background. The nurse practitioner role has been implemented internationally as a service reform model to improve the access and timeliness of health care. There is a substantial body of research into the nurse practitioner role and service outcomes, but scant information on the pattern of nurse practitioner work and how this is influenced by different service models. --------- Methods: We used work sampling methods. Data were collected between July 2008 and January 2009. Observations were recorded from a random sample of 30 nurse practitioners at 10-minute intervals in 2-hour blocks randomly generated to cover two weeks of work time from a sampling frame of six weeks. --------- Results: A total of 12,189 individual observations were conducted with nurse practitioners across Australia. Thirty individual activities were identified as describing nurse practitioner work, and these were distributed across three categories. Direct care accounted for 36.1% of how nurse practitioners spend their time, indirect care accounted for 32.2% and service-related activities made up 31.9%. --------- Conclusion. These findings provide useful baseline data for evaluation of nurse practitioner positions and the service effect of these positions. However, the study also raises questions about the best use of nurse practitioner time and the influences of barriers to and facilitators of this model of service innovation.

The application of a profluorescent nitroxide probe to detect reactive oxygen species derived from combustion-generated particulate matter

Particulate pollution has been widely recognised as an important risk factor to human health. In addition to increases in respiratory and cardiovascular morbidity associated with exposure to particulate matter (PM), WHO estimates that urban PM causes 0.8 million premature deaths globally and that 1.5 million people die prematurely from exposure to indoor smoke generated from the combustion of solid fuels. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. Oxidative stress caused by generation of free radicals and related reactive oxygen species (ROS) at the sites of deposition has been proposed as a mechanism for many of the adverse health outcomes associated with exposure to PM. In addition to particle-induced generation of ROS in lung tissue cells, several recent studies have shown that particles may also contain ROS. As such, they present a direct cause of oxidative stress and related adverse health effects. Cellular responses to oxidative stress have been widely investigated using various cell exposure assays. However, for a rapid screening of the oxidative potential of PM, less time-consuming and less expensive, cell-free assays are needed. The main aim of this research project was to investigate the application of a novel profluorescent nitroxide probe, synthesised at QUT, as a rapid screening assay in assessing the oxidative potential of PM. Considering that this was the first time that a profluorescent nitroxide probe was applied in investigating the oxidative stress potential of PM, the proof of concept regarding the detection of PM–derived ROS by using such probes needed to be demonstrated and a sampling methodology needed to be developed. Sampling through an impinger containing profluorescent nitroxide solution was chosen as a means of particle collection as it allowed particles to react with the profluorescent nitroxide probe during sampling, avoiding in that way any possible chemical changes resulting from delays between the sampling and the analysis of the PM. Among several profluorescent nitroxide probes available at QUT, bis(phenylethynyl)anthracene-nitroxide (BPEAnit) was found to be the most suitable probe, mainly due to relatively long excitation and emission wavelengths (λex= 430 nm; λem= 485 and 513 nm). These wavelengths are long enough to avoid overlap with the background fluorescence coming from light absorbing compounds which may be present in PM (e.g. polycyclic aromatic hydrocarbons and their derivatives). Given that combustion, in general, is one of the major sources of ambient PM, this project aimed at getting an insight into the oxidative stress potential of combustion-generated PM, namely cigarette smoke, diesel exhaust and wood smoke PM. During the course of this research project, it was demonstrated that the BPEAnit probe based assay is sufficiently sensitive and robust enough to be applied as a rapid screening test for PM-derived ROS detection. Considering that for all three aerosol sources (i.e. cigarette smoke, diesel exhaust and wood smoke) the same assay was applied, the results presented in this thesis allow direct comparison of the oxidative potential measured for all three sources of PM. In summary, it was found that there was a substantial difference between the amounts of ROS per unit of PM mass (ROS concentration) for particles emitted by different combustion sources. For example, particles from cigarette smoke were found to have up to 80 times less ROS per unit of mass than particles produced during logwood combustion. For both diesel and wood combustion it has been demonstrated that the type of fuel significantly affects the oxidative potential of the particles emitted. Similarly, the operating conditions of the combustion source were also found to affect the oxidative potential of particulate emissions. Moreover, this project has demonstrated a strong link between semivolatile (i.e. organic) species and ROS and therefore, clearly highlights the importance of semivolatile species in particle-induced toxicity.

An efficient approach for the direct synthesis of lithium niobate powders

Lithium niobate powders from the raw powders of Li2 O5 are directly synthesized by a combustion method with urea fuel. The synthesis parameters (e.g. the calcination temperature, calcination time, and urea-to-(Li2 CO3 + Nb2 O5) quantity ratio) are studied to reveal the optimized synthesis conditions for preparing high-quality lithium niobate powders. In our present work, it is found that a urea-to-(Li2 CO3 + Nb2 O5) ratio close to 3, calcination temperature at 550-600 degrees and reaction time around 2.5h may lead to high-quality lithium niobate powsers. The microstructure of synthesized powders is further studied; a possible mechanism of the involved reactions is also proposed.

Direct fabrication as a patient-targeted therapeutic in a clinical environment

A paradigm shift is taking place in orthopaedic and reconstructive surgery. This transition from using medical devices and tissue grafts towards the utilization of a tissue engineering approach combines biodegradable scaffolds with cells and/or biological molecules in order to repair and/or regenerate tissues. One of the potential benefits offered by solid freeform fabrication (SFF) technologies is the ability to create such biodegradable scaffolds with highly reproducible architecture and compositional variation across the entire scaffold due to their tightly controlled computer-driven fabrication. Many of these biologically activated materials can induce bone formation at ectopic and orthotopic sites, but they have not yet gained widespread use due to several continuing limitations, including poor mechanical properties, difficulties in intraoperative handling, lack of porosity suitable for cellular and vascular infiltration, and suboptimal degradation characteristics. In this chapter, we define scaffold properties and attempt to provide some broad criteria and constraints for scaffold design and fabrication in combination with growth factors for bone engineering applications. Lastly, we comment on the current and future developments in the field, such as the functionalization of novel composite scaffolds with combinations of growth factors designed to promote cell attachment, cell survival, vascular ingrowth, and osteoinduction.

The El Chichon stratospheric cloud : solid particulates and settling rates

Sampling of the El Chichón stratospheric cloud in early May and in late July, 1982, showed that a significant proportion of the cloud consisted of solid particles between 2 μm and 40 μm size. In addition, many particles may have been part of larger aggregates or clusters that ranged in size from < 10 μm to > 50 μm. The majority of individual grains were angular aluminosilicate glass shards with various amounts of smaller, adhering particles. Surface features on individual grains include sulfuric acid droplets and larger (0.5 μm to 1 μm) sulfate gel droplets with various amounts of Na, Mg, Ca and Fe. The sulfate gels probably formed by the interaction of sulfur-rich gases and solid particles within the cloud soon after eruption. Ca-sulfate laths may have formed by condensation within the plume during eruption, or alternatively, at a later stage by the reaction of sulfuric acid aerosols with ash fragments within the stratospheric cloud. A Wilson-Huang formulation for the settling rate of individual particles qualitatively agrees with the observed particle-size distribution for a period at least four months after injection of material into the stratosphere. This result emphasizes the importance of particle shape in controlling the settling rate of volcanic ash from the stratosphere.

Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives : A review

The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis. (C) 2013 Elsevier B. V. All rights reserved.

Characterisation of the micro-architecture of direct writing melt electrospun tissue engineering scaffolds using diffusion tensor and computed tomography microimaging

This article describes the first steps toward comprehensive characterization of molecular transport within scaffolds for tissue engineering. The scaffolds were fabricated using a novel melt electrospinning technique capable of constructing 3D lattices of layered polymer fibers with well - defined internal microarchitectures. The general morphology and structure order was then determined using T 2 - weighted magnetic resonance imaging and X - ray microcomputed tomography. Diffusion tensor microimaging was used to measure the time - dependent diffusivity and diffusion anisotropy within the scaffolds. The measured diffusion tensors were anisotropic and consistent with the cross - hatched geometry of the scaffolds: diffusion was least restricted in the direction perpendicular to the fiber layers. The results demonstrate that the cross - hatched scaffold structure preferentially promotes molecular transport vertically through the layers ( z - axis), with more restricted diffusion in the directions of the fiber layers ( x – y plane). Diffusivity in the x – y plane was observed to be invariant to the fiber thickness. The characteristic pore size of the fiber scaffolds can be probed by sampling the diffusion tensor at multiple diffusion times. Prospective application of diffusion tensor imaging for the real - time monitoring of tissue maturation and nutrient transport pathways within tissue engineering scaffolds is discussed.

Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs

In this paper, we have synthesized two novel diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) copolymers poly{3,6-dithiophene-2-yl-2,5-di(2-octyl)- pyrrolo[3,4-c]pyrrole-1,4-dione-alt-1,5-bis(dodecyloxy)naphthalene} (PDPPT-NAP) and poly{3,6-dithiophene-2-yl-2,5-di(2-butyldecyl)-pyrrolo[3,4-c]pyrrole-1,4- dione-alt-2-dodecyl-2H-benzo[d][1,2,3]triazole} (PDPPT-BTRZ) via direct arylation organometallic coupling. Both copolymers contain a common electron withdrawing DPP building block which is combined with electron donating alkoxy naphthalene and electron withdrawing alkyl-triazole comonomers. The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) for polymer PDPPT-NAP is around 23 400 g mol-1 whereas for polymer PDPPT-BTRZ it is 18 600 g mol-1. The solid state absorption spectra of these copolymers show a wide range of absorption from 400 nm to 1000 nm with optical band gaps calculated from absorption cut off values in the range of 1.45-1.30 eV. The HOMO values determined for PDPPT-NAP and PDPPT-BTRZ copolymers from photoelectron spectroscopy in air (PESA) data are 5.15 eV and 5.25 eV respectively. These polymers exhibit promising p-channel and ambipolar behaviour when used as an active layer in organic thin-film transistor (OTFT) devices. The highest hole mobility measured for polymer PDPPT-NAP is around 0.0046 cm2 V-1 s-1 whereas the best ambipolar performance was calculated for PDPPT-BTRZ with a hole and electron mobility of 0.01 cm2 V-1 s-1 and 0.006 cm2 V-1 s-1.