Ortho-Fluorination of azophenols increases the mesophase stability of photoresponsive hydrogen-bonded liquid crystals

Photoresponsive liquid crystals (LCs) whose alignment can be controlled with UV-Visible light are appealing for a range of photonic applications. From the perspective of exploring the interplay between the light response and the self-assembly of the molecular components, supramolecular liquid crystals are of particular interest. They allow elaborating the structure-property relationships that govern the optical performance of LC materials by subtle variation of the chemical structures of the building blocks. Herein we present a supramolecular system comprising azophenols and stilbazoles as hydrogen-bond donors and acceptors, respectively, and show that ortho-fluorination of the azophenol dramatically increases the thermal stability of the LC phases, an important characteristics in their further utilization in photonics. The systems exhibit fast photoinduced order-disorder transitions, and rapid recovery of the liquid-crystalline state once the light irradiation is ceased, due to the photochemical properties of azophenols

Effect of drying on the reproducibility of DIAGNOdent to detect caries-like lesions

The aim of this study was to verify the drying effect on the reproducibility of DIAGNOdent (Dd) devices to detect caries-like lesions. Three areas were created in each of the 34 bovine incisors: sound (S), demineralized (DE) and remineralized (RE). One examiner measured each area with two Dd devices (denominated X and Y), twice under humid, and twice under dry condition. Intra-rater agreement according each device and inter-device agreement were estimated by kappa statistics (k). Intra-rater agreement for device Y was substantial under humid (k DE=0.68 and k RE+S=0.68) and dry condition (k DE=0.64 and k RE+S=0.67). For device X, it was substantial under humid condition (k DE=0.57 and k RE+S=0.49), and it was almost perfect after air drying (k DE=1.0 and kRE+S=1.0). Inter-device agreement was slight (k =0.17) under humid condition, and it was substantial under dry condition (k =0.62). As reproducibility increased under dry condition, drying is advised to detect caries-like lesions on free smooth surfaces when different devices are used.Este estudo verificou o efeito da secagem sobre o resultado de reprodutibilidade de aparelhos laser DIAGNOdent (Dd) no diagnóstico de cárie artificial. Três áreas foram produzidas em cada um dos 34 incisivos bovinos: hígida (S), desmineralizada (DE) e remineralizada (RE). Um examinador mediu cada área com dois aparelhos Dd (denominados X e Y), sendo duas vezes sob a condição úmida e duas vezes sob a condição seca. A concordância intra-examinador segundo cada aparelho, e a concordância entre aparelhos foram estimadas por meio da estatística kappa (k). A reprodutibilidade intra para o aparelho Y foi substancial sob a condição úmida (kDE=0,68 e k RE+S=0,68) e seca (k DE=0,64 e k RE+S=0,67). Para o aparelho X, a concordância foi substancial sob a condição úmida (kDE=0,57 e k RE+S=0,49) e foi quase perfeita após a secagem (kDE=1,0 e k RE+S+1,0). A concordância entre aparelhos foi fraca (k=0,17) na condição úmida, porém foi substancial na condição seca (k=0,62). Como a reprodutibilidade foi melhor sob a condição seca, a secagem da superfície dentária é aconselhada para se detectar lesões de cárie incipientes em superfícies lisas livres, quando mais de um aparelho é utilizado no diagnóstico

Combined use of ISCR and biostimulation techniques in incomplete processes of reductive dehalogenation of chlorinated solvents

Pools of chloroethenes are more recalcitrant in the transition zone between aquifers and basal aquitards than those elsewhere in the aquifer. Although biodegradation of chloroethenes occur in this zone, it is a slow process and a remediation strategy is needed. The aim of this study was to demonstrate that combined strategy of biostimulation and in situ chemical reduction (ISCR) is more efficient than the two separated strategies. Four different microcosm experiments with sediment and groundwater of a selected field site where an aged perchloroethene (PCE)-pool exists at the bottom of a transition zone, were designed under i) natural conditions, ii) biostimulation with lactic acid, iii) in situ chemical reduction (ISCR)with zero valent iron (ZVI) and under iv) a combined strategy with lactic acid and ZVI. Biotic and abiotic dehalogenation, terminal electron acceptor processes and evolution of microbial communities were investigated for each experiment. The main results where: i) limited reductive dehalogenation of PCE occurs under sulfate-reducing conditions; ii) biostimulation with lactic acid promotes a more pronounced reductive dehalogenation of PCE in comparison under natural conditions, but resulted in an accumulation of cis-dichloroethene (cDCE); iii) ISCR with zero-valent iron (ZVI) facilitates a sustained dehalogenation of PCE and its metabolites to non-halogenated products, however, the iv) combined strategy results in the fastest and sustained dehalogenation of PCE to non-halogenated products in comparison of all four set-ups. These findings suggest that biostimulation and ISCRwith ZVI are the most suitable strategy for a complete reductive dehalogenation of PCE-pools in the transition zone

More Than Just Adolescence: Differences in Fatigue Between Youth With Cerebral Palsy and Typically Developing Peers

Objective To quantify differences in fatigue and disordered sleep between adolescents with cerebral palsy (CP) and their typically developing peers. A secondary aim was to investigate the association between fatigue and disordered sleep in adolescents with CP. Methods A convenience sample of 36 youth with CP aged 10-18 years was matched for age and sex with 36 typically developing peers. The Fatigue Impact and Severity Self-Assessment (FISSA), the Patient-Reported Outcome Measurement Information System (PROMIS) fatigue profile, and the Sleep Disturbance Scale for Children (SDSC) were collected. Results Higher fatigue was reported in participants with CP than in their typically developing peers based on the FISSA total score (mean paired difference=19.06; 99% confidence interval [CI], 6.06-32.1), the FISSA impact subscale (mean paired difference=11.19; 99% CI, 3.96-18.4), and the FISSA Management and Activity Modification subscale (mean paired difference=7.86; 99% CI, 1.1-14.6). There were no differences between groups in the PROMIS fatigue profile (mean paired difference=1.63; 99% CI, -1.57-4.83) or the SDSC total score (mean paired difference=2.71; 99% CI, -2.93-8.35). Conclusion Youth with CP experienced significantly more fatigue than their peers as assessed by a comprehensive measure that considered both general and diagnosis-specific concerns. Sleep did not differ between youth with CP and their typically developing peers. These findings underscore the need to consider the clinical management of fatigue across the lifespan of individuals with CP to prevent the associated deterioration of functional abilities

The role of ecotones in the dehalogenation of chloroethenes in alluvial fan aquifers

The presence of ecotones in transition zones between geological strata (e.g. layers of gravel and sand interbedded with layers of silt in distal alluvial fan deposits) in aquifers plays a significant role in regulating the flux of matter and energy between compartments. Ecotones are characterised by steep physicochemical and biological gradients and considerable biological diversity. However, the link between organic pollutants and degradation potential in ecotones has scarcely been studied. The aim of this study is to relate the presence of ecotones with the dehalogenation of chloroethenes. A field site was selected where chloroethene contamination occurs in a granular aquifer with geological heterogeneities. The site is monitored by multilevel and conventional wells. Groundwater samples were analysed by chemical, isotopic, and molecular techniques. The main results were as follows: (1) two ecotones were characterised in the source area, one in the upper part of the aquifer and the second in the transition zone to the bottom aquitard, where the aged pool is located; (2) the ecotone located in the transition zone to the bottom aquitard has greater microbial diversity, due to higher geological heterogeneities; (3) both ecotones show the reductive dehalogenation of perchloroethylene and trichloroethylene; and (4) these ecotones are the main zones of the reductive dehalogenation of the pollutants, given the more reductive conditions at the centre of the plume. These findings suggest that ecotones are responsible for natural attenuation, where oxic conditions prevailed at the aquifer and bioremediation strategies could be applied more effectively in these zones to promote complete reductive dehalogenation

Reductive dechlorination in recalcitrant sources of chloroethenes in the transition zone between aquifers and aquitards

In the transition zone between aquifers and basal aquitards, the perchloroethene pools at an early time in their evolution are more recalcitrant than those elsewhere in the aquifer. The aim of this study is to demonstrate that the biodegradation of chloroethenes from aged pools (i.e., pools after decades of continuous groundwater flushing and dissolution) of perchloroethene is favored in the transition zone. A field site was selected where an aged pool exists at the bottom of a transition zone. Two boreholes were drilled to obtain sediment and groundwater samples to perform chemical, isotopic, molecular, and clone library analyses and microcosm experiments. The main results were as follows: (i) the transition zone is characterized by a high microbial richness; (ii) reductively dechlorinating microorganisms are present and partial reductive dechlorination coexists with denitrification, Fe and Mn reduction, and sulfate reduction; (iii) reductively dechlorinating microorganisms were also present in the zone of the aged pool; (v) the high concentrations of perchloroethene in this zone resulted in a decrease in microbial richness; (vi) however, the presence of fermenting microorganisms supplying electrons for the reductively dechlorinating microorganisms prevented the reductive dechlorination to be inhibited. These findings suggest that biostimulation and/or bioaugmentation could be applied to promote complete reductive dechlorination and to enhance the dissolution of more nonaqueous phase liquids (DNAPL)

Analysis of Agglomerative Clustering

The diameter $k$-clustering problem is the problem of partitioning a finite subset of $\mathbb{R}^d$ into $k$ subsets called clusters such that the maximum diameter of the clusters is minimized. One early clustering algorithm that computes a hierarchy of approximate solutions to this problem (for all values of $k$) is the agglomerative clustering algorithm with the complete linkage strategy. For decades, this algorithm has been widely used by practitioners. However, it is not well studied theoretically. In this paper, we analyze the agglomerative complete linkage clustering algorithm. Assuming that the dimension $d$ is a constant, we show that for any $k$ the solution computed by this algorithm is an $O(\log k)$-approximation to the diameter $k$-clustering problem. Our analysis does not only hold for the Euclidean distance but for any metric that is based on a norm. Furthermore, we analyze the closely related $k$-center and discrete $k$-center problem. For the corresponding agglomerative algorithms, we deduce an approximation factor of $O(\log k)$ as well.Comment: A preliminary version of this article appeared in Proceedings of the 28th International Symposium on Theoretical Aspects of Computer Science (STACS '11), March 2011, pp. 308-319. This article also appeared in Algorithmica. The final publication is available at http://link.springer.com/article/10.1007/s00453-012-9717-

MODELLING ERRORS IN X-RAY FLUOROSCOPIC IMAGING SYSTEMS USING PHOTOGRAMMETRIC BUNDLE ADJUSTMENT WITH A DATA-DRIVEN SELF-CALIBRATION APPROACH

X-ray imaging is a fundamental tool of routine clinical diagnosis. Fluoroscopic imaging can further acquire X-ray images at video frame rates, thus enabling non-invasive in-vivo motion studies of joints, gastrointestinal tract, etc. For both the qualitative and quantitative analysis of static and dynamic X-ray images, the data should be free of systematic biases. Besides precise fabrication of hardware, software-based calibration solutions are commonly used for modelling the distortions. In this primary research study, a robust photogrammetric bundle adjustment was used to model the projective geometry of two fluoroscopic X-ray imaging systems. However, instead of relying on an expert photogrammetrist’s knowledge and judgement to decide on a parametric model for describing the systematic errors, a self-tuning data-driven approach is used to model the complex non-linear distortion profile of the sensors. Quality control from the experiment showed that 0.06 mm to 0.09 mm 3D reconstruction accuracy was achievable post-calibration using merely 15 X-ray images. As part of the bundle adjustment, the location of the virtual fluoroscopic system relative to the target field can also be spatially resected with an RMSE between 3.10 mm and 3.31 mm