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.

Plasma-enabled graded nanotube biosensing arrays on a Si nanodevice platform : catalyst-free integration and in situ detection of nucleation events

Low-temperature plasmas in direct contact with arbitrary, written linear features on a Si wafer enable catalyst-free integration of carbon nanotubes into a Si-based nanodevice platform and in situ resolution of individual nucleation events. The graded nanotube arrays show reliable, reproducible, and competitive performance in electron field emission and biosensing nanodevices.

Confidence measurement in the light of signal detection theory

We compare three alternative methods for eliciting retrospective confidence in the context of a simple perceptual task: the Simple Confidence Rating (a direct report on a numerical scale), the Quadratic Scoring Rule (a post-wagering procedure), and the Matching Probability (MP; a generalization of the no-loss gambling method). We systematically compare the results obtained with these three rules to the theoretical confidence levels that can be inferred from performance in the perceptual task using Signal Detection Theory (SDT). We find that the MP provides better results in that respect. We conclude that MP is particularly well suited for studies of confidence that use SDT as a theoretical framework.

Noise Filtering of Process Execution Logs based on Outliers Detection

This paper presents a technique for the automated removal of noise from process execution logs. Noise is the result of data quality issues such as logging errors and manifests itself in the form of infrequent process behavior. The proposed technique generates an abstract representation of an event log as an automaton capturing the direct follows relations between event labels. This automaton is then pruned from arcs with low relative frequency and used to remove from the log those events not fitting the automaton, which are identified as outliers. The technique has been extensively evaluated on top of various auto- mated process discovery algorithms using both artificial logs with different levels of noise, as well as a variety of real-life logs. The results show that the technique significantly improves the quality of the discovered process model along fitness, appropriateness and simplicity, without negative effects on generalization. Further, the technique scales well to large and complex logs.

A recurrent network in the lateral amygdala: A mechanism for temporal coincidence detection

The dorsal lateral amygdala (LAd) is a vital nucleus for the formation of associations between aversive unconditioned stimuli (US) and neutral stimuli, such as auditory tones, which can become conditioned (CS) to the US through temporal pairing. Important aspects of CS-US associations are believed to occur within the LAd, however relatively little is known about the temporal behavior of local LAd networks. Information about the CS and US enters the LA via a rapid and direct thalamic input and a longer latency cortical path...

Is the sun too bright in Queensland? An approach to robust outdoor colour beacon detection

Using cameras onboard a robot for detecting a coloured stationary target outdoors is a difficult task. Apart from the complexity of separating the target from the background scenery over different ranges, there are also the inconsistencies with direct and reflected illumination from the sun,clouds, moving and stationary objects. They can vary both the illumination on the target and its colour as perceived by the camera. In this paper, we analyse the effect of environment conditions, range to target, camera settings and image processing on the reported colours of various targets. The analysis indicates the colour space and camera configuration that provide the most consistent colour values over varying environment conditions and ranges. This information is used to develop a detection system that provides range and bearing to detected targets. The system is evaluated over various lighting conditions from bright sunlight, shadows and overcast days and demonstrates robust performance. The accuracy of the system is compared against a laser beacon detector with preliminary results indicating it to be a valuable asset for long-range coloured target detection.

Investigations of an electrochemical platform based on the layered MoS2-graphene and horseradish peroxidase nanocomposite for direct electrochemistry and electrocatalysis

The self-assembly of layered molybdenum disulfide–graphene (MoS2–Gr) and horseradish peroxidase (HRP) by electrostatic attraction into a novel hybrid nanomaterial (HRP–MoS2–Gr) is reported. The properties of the MoS2–Gr were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (TEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). UV–vis and Fourier transform infrared spectroscopy (FT-IR) indicate that the native structure of the HRP is maintained after the assembly, implying good biocompatibility of MoS2–Gr nanocomposite. Furthermore, the HRP–MoS2–Gr composite is utilized as a biosensor, which displays electrocatalytic activity to hydrogen peroxide (H2O2) with high sensitivity (679.7 μA mM−1 cm−2), wide linear range (0.2 μM–1.103 mM), low detection limit (0.049 μM), and fast amperometric response. In addition, the biosensor also exhibits strong anti-interference ability, satisfactory stability and reproducibility. These desirable electrochemical properties are attributed to the good biocompatibility and electron transport efficiency of the MoS2–Gr composite, as well as the high loading of HRP. Therefore, this biosensor is potentially suitable for H2O2 analysis in environmental, pharmaceutical, food or industrial applications.

Rapid isolation and detection of erythropoietin in blood plasma by magnetic core gold nanoparticles and portable Raman spectroscopy

Isolating, purifying, and identifying proteins in complex biological matrices is often difficult, time consuming, and unreliable. Herein we describe a rapid screening technique for proteins in biological matrices that combines selective protein isolation with direct surface enhanced Raman spectroscopy (SERS) detection. Magnetic core gold nanoparticles were synthesised, characterised, and subsequently functionalized with recombinant human erythropoietin (rHuEPO)-specific antibody. The functionalized nanoparticles were used to capture rHuEPO from horse blood plasma within 15 minutes. The selective binding between the protein and the functionalized nanoparticles was monitored by SERS. The purified protein was then released from the nanoparticles’ surface and directly spectroscopically identified on a commercial nanopillar SERS substrate. ELISA independently confirmed the SERS identification and quantified the released rHuEPO. Finally, the direct SERS detection of the extracted protein was successfully demonstrated for in-field screening by a handheld Raman spectrometer within 1 minute sample measurement time.

Teledermatology: Its use in the detection and management of actinic keratosis

Teledermatology can profoundly improve access to medical services for those who may have limited access to dermatology due to workforce shortages, distance to providers, or limitations in their mobility. Two common ways of teledermatology are differentiated: life synchronous, where patient and doctor communicate directly, or store and forward asynchronous methods, where the patient and doctor provide and assess the medical information independently. Teledermatology has been tested for its safety, feasibility and accuracy for a number of dermatological conditions, including the early detection of skin cancer and is usually safe, feasible and accurate. Studies reported somewhat better results for synchronous than asynchronous methods, possibly because of loss of information if no direct patient doctor contact is feasible. However asynchronous methods are easier to organize, require less sophisticated technology and are more widely accessible, and are more convenient for both patients and doctors. No study to date focused solely on teledermatology of actinic keratosis, but such lesions are typically found during teledermatology examinations for other main target lesions. In studies where such results were reported, actinic keratoses seemed to be readily identifiable for teledermatologists and adequate management and treatment can be suggested within remote consultations.