Development of a baseline-temperature correction methodology for electrochemical sensors and its implications for long-term stability

Recent studies have shown that (three-electrode) electrochemical sensors can be utilised for air quality monitoring and exposure assessment. The long-term performance of these sensors is however, often limited by the effects of ambient meteorological parameters on the sensor baseline, in particular temperature. If electrochemical (EC) sensors are to be adopted for air quality measurement over extended periods (months), this effect must be accounted for. Recent long-term, ambient measurements of CO, NO and NO$_2$ using EC sensors have revealed that temperature (and relative humidity (RH)) had an effect on the baseline which was more pronounced in the case of NO sensors with coefficient of determination, $R^2$ of 0.9 when compared to CO and NO$_2$ with $R^2$ < 0.2. In this paper we present a correction methodology that quantifies this effect (referred to here as fitted baseline), implementing these correction on the EC measurements. We found that EC sensors corrected for baseline-temperature effect using the method describe in this paper show good agreement when compared with traditional reference instrument. The coefficient of determination $R^2$ of 0.7-0.8 and gradient of 0.9 was observed for baseline-temperature corrected NO compared to $R^2$ = 0.02 prior to baseline-temperature correction. Furthermore, the correction methodology was validated by comparing the temperature-baseline with proxy temperature compensating measurements obtained from the fourth electrode of a set of novel four-electrode electrochemical sensors. A good agreement (R$^2$ = 0.9, with gradients = 0.7-1.08 for NO and 0.5 < R$^2$ < 0.73 for CO) was observed between temperature fitted baselines and outputs from the fourth electrodes (also known non-sensing/auxiliary electrode). Meanwhile, the long-term stability (calibrated signal output) of temperature-corrected data was evaluated by comparing the change in sensor gain to meteorological parameters including temperature, relative humidity, wind speed and wind direction. The results showed that there was no statistically significant change in sensitivity (two-sided $t$-test, p = 0.34) of the temperature-corrected electrochemical sensor with respect to these parameters (over several months). This work demonstrates that using the baseline-temperature correction methodology described in this paper, electrochemical sensors can be used for long-term (months), quantitative measurements of air quality gases at the parts per billion volume (ppb) mixing ratio level typical of ambient conditions in the urban environment.The authors would like to thank Cambridge Commonwealth Trust & Cambridge Overseas Trust and Dorothy Hodgkin Studentship for the PhD studentship awarded to Olalekan Popoola. We will like to thank NERC for funding the SNAQ Heathrow project as well as DfT and EPSRC for funding the MESSAGE project

Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp(3))-H functionalization of amines

Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular α-functionalization reactions of different tertiary amines, generating C(sp3)-C(sp3/sp2/sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the α-C-H bond via intramolecular 1,5-hydride transfer onto the aryne, which leads to activation of a range of integrated pronucleophiles and ultimately affords a new approach to cross-dehydrogenative coupling reactions which utilize aryne intermediates

A common periodic representation of interaural time differences in mammalian cortex

Binaural hearing, the ability to detect small differences in the timing and level of sounds at the two ears, underpins the ability to localize sound sources along the horizontal plane, and is important for decoding complex spatial listening environments into separate objects - a critical factor in 'cocktail-party listening'. For human listeners, the most important spatial cue is the interaural time difference (ITD). Despite many decades of neurophysiological investigations of ITD sensitivity in small mammals, and computational models aimed at accounting for human perception, a lack of concordance between these studies has hampered our understanding of how the human brain represents and processes ITDs. Further, neural coding of spatial cues might depend on factors such as head-size or hearing range, which differ considerably between humans and commonly used experimental animals. Here, using magnetoencephalography (MEG) in human listeners, and electro-corticography (ECoG) recordings in guinea pig-a small mammal representative of a range of animals in which ITD coding has been assessed at the level of single-neuron recordings-we tested whether processing of ITDs in human auditory cortex accords with a frequency-dependent periodic code of ITD reported in small mammals, or whether alternative or additional processing stages implemented in psychoacoustic models of human binaural hearing must be assumed. Our data were well accounted for by a model consisting of periodically tuned ITD-detectors, and were highly consistent across the two species. The results suggest that the representation of ITD in human auditory cortex is similar to that found in other mammalian species, a representation in which neural responses to ITD are determined by phase differences relative to sound frequency rather than, for instance, the range of ITDs permitted by head size or the absolute magnitude or direction of ITD

In the face of threat: neural and endocrine correlates of impaired facial emotion recognition in cocaine dependence.

The ability to recognize facial expressions of emotion in others is a cornerstone of human interaction. Selective impairments in the recognition of facial expressions of fear have frequently been reported in chronic cocaine users, but the nature of these impairments remains poorly understood. We used the multivariate method of partial least squares and structural magnetic resonance imaging to identify gray matter brain networks that underlie facial affect processing in both cocaine-dependent (n = 29) and healthy male volunteers (n = 29). We hypothesized that disruptions in neuroendocrine function in cocaine-dependent individuals would explain their impairments in fear recognition by modulating the relationship with the underlying gray matter networks. We found that cocaine-dependent individuals not only exhibited significant impairments in the recognition of fear, but also for facial expressions of anger. Although recognition accuracy of threatening expressions co-varied in all participants with distinctive gray matter networks implicated in fear and anger processing, in cocaine users it was less well predicted by these networks than in controls. The weaker brain-behavior relationships for threat processing were also mediated by distinctly different factors. Fear recognition impairments were influenced by variations in intelligence levels, whereas anger recognition impairments were associated with comorbid opiate dependence and related reduction in testosterone levels. We also observed an inverse relationship between testosterone levels and the duration of crack and opiate use. Our data provide novel insight into the neurobiological basis of abnormal threat processing in cocaine dependence, which may shed light on new opportunities facilitating the psychosocial integration of these patients.This work was funded by a research grant from the Medical Research Council (G0701497) and supported by the infrastructure of the Behavioural and Clinical Neuroscience Institute (which is supported by a joint award from the Medical Research Council and the Wellcome Trust). This study was jointly sponsored by the Cambridge University Hospitals NHS Foundation Trust and the University of Cambridge. KD Ersche, CC Hagan, and PS Jones are supported by the Medical Research Council, and DG Smith by the Cambridge Overseas Trust.This is the final version of the article. It first appeared from NPG via http://dx.doi.org/10.1038/tp.2015.5

The Natsal-SF measure of sexual function: comparison of three scoring methods

The Natsal-SF is a psychometrically-validated measure of sexual function for use in community health surveys, derived from 17 questions reflecting three components of sexual function. Scoring requires knowledge of complex statistical modelling and, given the methodological complexities, we assess the validity of two simplified scoring methods calculated using the factor loadings produced when originally modelling the Natsal-SF items. Method 1 uses these factor loadings to three decimal places while method 2 assigns whole numbers to each item based on the factor loadings. Scores from these simplified methods are compared to the original score using correlation coefficients, by comparing the distributions, and the scores of each method in a linear regression model with key variables. We found scores from the simplified methods both correlate highly with the original score, and the distributions of scores closely match. The simplified methods result in different regression coefficients for gender and relationship context, but estimate the coefficients of all other variables similarly to the original method. While the Natsal-SF should ideally be scored using latent variable modelling, the simplified methods perform well so can be used in similar contexts, increasing the utility of the Natsal-SF and enabling future studies to measure sexual function more comprehensively

Source attribution of air pollution by spatial scale separation using high spatial density networks of low cost air quality sensors

To carry out detailed source attribution for air quality assessment it is necessary to distinguish pollutant contributions that arise from local emissions from those attributable to non-local or regional emission sources. Frequently this requires the use of complex models and inversion methods, prior knowledge or assumptions regarding the pollution environment. In this paper we demonstrate how high spatial density and fast response measurements from low-cost sensor networks may facilitate this separation. A purely measurement-based approach to extract underlying pollution levels (baselines) from the measurements is presented exploiting the different relative frequencies of local and background pollution variations. This paper shows that if high spatial and temporal coverage of air quality measurements are available, the different contributions to the total pollution levels, namely the regional signal as well as near and far field local sources, can be quantified. The advantage of using high spatial resolution observations, as can be provided by low-cost sensor networks, lies in the fact that no prior assumptions about pollution levels at individual deployment sites are required. The methodology we present here, utilising measurements of carbon monoxide (CO), has wide applicability, including additional gas phase species and measurements obtained using reference networks. While similar studies have been performed, this is the first study using networks at this density, or using low cost sensor networks.The authors thank EPSRC (EP/E001912/1) for funding for the Message project. IH thanks the German National Academic Foundation for funding of MPhil degree.This is the final published version. It first appeared at http://www.sciencedirect.com/science/article/pii/S1352231015300583#

Comparative Morphology of the Penis and Clitoris in Four Species of Moles (Talpidae).

The penile and clitoral anatomy of four species of Talpid moles (broad-footed, star-nosed, hairy-tailed, and Japanese shrew moles) were investigated to define penile and clitoral anatomy and to examine the relationship of the clitoral anatomy with the presence or absence of ovotestes. The ovotestis contains ovarian tissue and glandular tissue resembling fetal testicular tissue and can produce androgens. The ovotestis is present in star-nosed and hairy-tailed moles, but not in broad-footed and Japanese shrew moles. Using histology, three-dimensional reconstruction, and morphometric analysis, sexual dimorphism was examined with regard to a nine feature masculine trait score that included perineal appendage length (prepuce), anogenital distance, and presence/absence of bone. The presence/absence of ovotestes was discordant in all four mole species for sex differentiation features. For many sex differentiation features, discordance with ovotestes was observed in at least one mole species. The degree of concordance with ovotestes was highest for hairy-tailed moles and lowest for broad-footed moles. In relationship to phylogenetic clade, sex differentiation features also did not correlate with the similarity/divergence of the features and presence/absence of ovotestes. Hairy-tailed and Japanese shrew moles reside in separated clades, but they exhibit a high degree of congruence. Broad-footed and hairy-tailed moles reside within the same clade but had one of the lowest correlations in features and presence/absence of ovotestes. Thus, phylogenetic affinity and the presence/absence of ovotestes are poor predictors for most sex differentiation features within mole external genitalia

Change in Composition of the Anopheles Gambiae Complex and its Possible Implications for the Transmission of Malaria and Lymphatic Filariasis in North-Eastern Tanzania.

A dramatic decline in the incidence of malaria due to Plasmodium falciparum infection in coastal East Africa has recently been reported to be paralleled (or even preceded) by an equally dramatic decline in malaria vector density, despite absence of organized vector control. As part of investigations into possible causes for the change in vector population density, the present study analysed the Anopheles gambiae s.l. sibling species composition in north-eastern Tanzania. The study was in two parts. The first compared current species complex composition in freshly caught An. gambiae s.l. complex from three villages to the composition reported from previous studies carried out 2-4 decades ago in the same villages. The second took advantage of a sample of archived dried An. gambiae s.l. complex specimens collected regularly from a fourth study village since 2005. Both fresh and archived dried specimens were identified to sibling species of the An. gambiae s.l. complex by PCR. The same specimens were moreover examined for Plasmodium falciparum and Wuchereria bancrofti infection by PCR. As in earlier studies, An. gambiae s.s., Anopheles merus and Anopheles arabiensis were identified as sibling species found in the area. However, both study parts indicated a marked change in sibling species composition over time. From being by far the most abundant in the past An. gambiae s.s. was now the most rare, whereas An. arabiensis had changed from being the most rare to the most common. P. falciparum infection was rarely detected in the examined specimens (and only in An. arabiensis) whereas W. bancrofti infection was prevalent and detected in all three sibling species. The study indicates that a major shift in An. gambiae s.l. sibling species composition has taken place in the study area in recent years. Combined with the earlier reported decline in overall malaria vector density, the study suggests that this decline has been most marked for An. gambiae s.s., and least for An. arabiensis, leading to current predominance of the latter. Due to differences in biology and vectorial capacity of the An. gambiae s.l. complex the change in sibling species composition will have important implications for the epidemiology and control of malaria and lymphatic filariasis in the study area

Disrupted iron regulation in the brain and periphery in cocaine addiction

Stimulant drugs acutely increase dopamine neurotransmission in the brain, and chronic use leads to neuroadaptive changes in the mesolimbic dopamine system and morphological changes in basal ganglia structures. Little is known about the mechanisms underlying these changes but preclinical evidence suggests that iron, a coenzyme in dopamine synthesis and storage, may be a candidate mediator. Iron is present in high concentrations in the basal ganglia and stimulant drugs may interfere with iron homeostasis. We hypothesised that morphological brain changes in cocaine addiction relate to abnormal iron regulation in the brain and periphery. We determined iron concentration in the brain, using quantitative susceptibility mapping, and in the periphery, using iron markers in circulating blood, in 44 patients with cocaine addiction and 44 healthy controls. Cocaine-addicted individuals showed excess iron accumulation in the globus pallidus, which strongly correlated with duration of cocaine use, and mild iron deficiency in the periphery, which was associated with low iron levels in the red nucleus. Our findings show that iron dysregulation occurs in cocaine addiction and suggest that it arises consequent to chronic cocaine use. Putamen enlargement in these individuals was unrelated to iron concentrations, suggesting that these are co-occurring morphological changes that may respectively reflect predisposition to, and consequences of cocaine addiction. Understanding the mechanisms by which cocaine affects iron metabolism may reveal novel therapeutic targets, and determine the value of iron levels in the brain and periphery as biomarkers of vulnerability to, as well as progression and response to treatment of cocaine addiction