Selective oxidative degradation of azo dyes by hydrogen peroxide catalysed by manganese(II) ions

Manganese(II) ions catalyse the oxidative degradation of Calmagite (H3CAL) dye in aqueous solution at 20 ± 1 °C in the pH range 7.5–9.0 using hydrogen peroxide (H2O2) as oxidant by a mechanism that involves strong complexation to the MnII centre. It is proposed that [MnIII(CAL)(O2H)]− i.e. a dye coordinated hydroperoxyl (O2H−) MnIII complex is formed and bleaching of the dye is initiated by an electron-transfer to MnIII, with the binding of H2O2 being the rate determining step. At pH 9.0 in (bi)carbonate, HCO3−, H3CAL is rapidly bleached via the in situ formation of coordinated peroxycarbonate (HCO4−); a TOF (TOF = moles of dye bleached per mole of manganese per hour) of ∼5000 h−1 can be achieved. The bleaching of the related azo dyes Orange II and Orange G is different because, unlike Calmagite, they lack an o,o-dihydroxy motif so are unable to complex strongly to MnII and no oxidation to MnIII occurs. At pH 8.0 (phosphate buffer) Orange II and Orange G are not bleached but bleaching can be achieved at pH 9.0 (HCO3− buffer); the rate determining step is dye coordination and it is proposed bleaching is achieved via an outer-sphere oxygen atom transfer. Mechanisms for dye bleaching at pH 8.0 and pH 9.0 are proposed using data from EPR, UV/VIS and ESI-MS. MnII/H2O2/HCO3− form a potent oxidising mixture that is capable of removing stubborn stains such as curcumin

CASTNet: Community-Attentive Spatio-Temporal Networks for Opioid Overdose Forecasting

Opioid overdose is a growing public health crisis in the United States. This crisis, recognized as "opioid epidemic," has widespread societal consequences including the degradation of health, and the increase in crime rates and family problems. To improve the overdose surveillance and to identify the areas in need of prevention effort, in this work, we focus on forecasting opioid overdose using real-time crime dynamics. Previous work identified various types of links between opioid use and criminal activities, such as financial motives and common causes. Motivated by these observations, we propose a novel spatio-temporal predictive model for opioid overdose forecasting by leveraging the spatio-temporal patterns of crime incidents. Our proposed model incorporates multi-head attentional networks to learn different representation subspaces of features. Such deep learning architecture, called "community-attentive" networks, allows the prediction of a given location to be optimized by a mixture of groups (i.e., communities) of regions. In addition, our proposed model allows for interpreting what features, from what communities, have more contributions to predicting local incidents as well as how these communities are captured through forecasting. Our results on two real-world overdose datasets indicate that our model achieves superior forecasting performance and provides meaningful interpretations in terms of spatio-temporal relationships between the dynamics of crime and that of opioid overdose.Comment: Accepted as conference paper at ECML-PKDD 201

Closing the Gaps: From Science to Action in Maternal, Newborn, and Child Health in Africa

As part of a series on maternal, neonatal, and child health in sub-Saharan Africa, Sara Bennett and Freddie Ssengooba discuss the challenges of getting science into policy in Africa

Measurements in two bases are sufficient for certifying high-dimensional entanglement

High-dimensional encoding of quantum information provides a promising method of transcending current limitations in quantum communication. One of the central challenges in the pursuit of such an approach is the certification of high-dimensional entanglement. In particular, it is desirable to do so without resorting to inefficient full state tomography. Here, we show how carefully constructed measurements in two bases (one of which is not orthonormal) can be used to faithfully and efficiently certify bipartite high-dimensional states and their entanglement for any physical platform. To showcase the practicality of this approach under realistic conditions, we put it to the test for photons entangled in their orbital angular momentum. In our experimental setup, we are able to verify 9-dimensional entanglement for a pair of photons on a 11-dimensional subspace each, at present the highest amount certified without any assumptions on the state.Comment: 11+14 pages, 2+7 figure

Dark Matter, Muon g-2 and Other SUSY Constraints

Recent developments constraining the SUSY parameter space are reviewed within the framework of SUGRA GUT models. The WMAP data is seen to reduce the error in the density of cold dark matter by about a factor of four, implying that the lightest stau is only 5 -10 GeV heavier than the lightest neutralino when m_0, m_{1/2} < 1 TeV. The CMD-2 re-analysis of their data has reduced the disagreement between the Standard Model prediction and the Brookhaven measurement of the muon magnetic moment to 1.9 sigma, while using the tau decay data plus CVC, the disagreement is 0.7 sigma. (However, the two sets of data remain inconsistent at the 2.9 sigma level.) The recent Belle and BABAR measurements of the B -> phi K CP violating parameters and branching ratios are discussed. They are analyzed theoretically within the BBNS improved factorization method. The CP parameters are in disagreement with the Standard Model at the 2.7 sigma level, and the branching ratios are low by a factor of two or more over most of the parameter space. It is shown that both anomalies can naturally be accounted for by adding a non-universal cubic soft breaking term at M_G mixing the second and third generations.Comment: 16 pages, 7 figures, plenary talk at Beyond The Desert '03, Castle Ringberg, Germany, June 9, 2003. Typos correcte

Body Temperature Patterns and Rhythmicity in Free-Ranging Subterranean Damaraland Mole-Rats, Fukomys damarensis

Body temperature (Tb) is an important physiological component that affects endotherms from the cellular to whole organism level, but measurements of Tb in the field have been noticeably skewed towards heterothermic species and seasonal comparisons are largely lacking. Thus, we investigated patterns of Tb patterns in a homeothermic, free-ranging small mammal, the Damaraland mole-rat (Fukomys damarensis) during both the summer and winter. Variation in Tb was significantly greater during winter than summer, and greater among males than females. Interestingly, body mass had only a small effect on variation in Tb and there was no consistent pattern relating ambient temperature to variation in Tb. Generally speaking, it appears that variation in Tb patterns varies between seasons in much the same way as in heterothermic species, just to a lesser degree. Both cosinor analysis and Fast Fourier Transform analysis revealed substantial individual variation in Tb rhythms, even within a single colony. Some individuals had no Tb rhythms, while others appeared to exhibit multiple rhythms. These data corroborate previous laboratory work showing multiplicity of rhythms in mole-rats and suggest the variation seen in the laboratory is a true indicator of the variation seen in the wild

Histidine Hydrogen-Deuterium Exchange Mass Spectrometry for Probing the Microenvironment of Histidine Residues in Dihydrofolate Reductase

Histidine Hydrogen-Deuterium Exchange Mass Spectrometry (His-HDX-MS) determines the HDX rates at the imidazole C(2)-hydrogen of histidine residues. This method provides not only the HDX rates but also the pK(a) values of histidine imidazole rings. His-HDX-MS was used to probe the microenvironment of histidine residues of E. coli dihydrofolate reductase (DHFR), an enzyme proposed to undergo multiple conformational changes during catalysis.Using His-HDX-MS, the pK(a) values and the half-lives (t(1/2)) of HDX reactions of five histidine residues of apo-DHFR, DHFR in complex with methotrexate (DHFR-MTX), DHFR in complex with MTX and NADPH (DHFR-MTX-NADPH), and DHFR in complex with folate and NADP+ (DHFR-folate-NADP+) were determined. The results showed that the two parameters (pK(a) and t(1/2)) are sensitive to the changes of the microenvironment around the histidine residues. Although four of the five histidine residues are located far from the active site, ligand binding affected their pK(a), t(1/2) or both. This is consistent with previous observations of ligand binding-induced distal conformational changes on DHFR. Most of the observed pK(a) and t(1/2) changes could be rationalized using the X-ray structures of apo-DHFR, DHFR-MTX-NADPH, and DHFR-folate-NADP+. The availability of the neutron diffraction structure of DHFR-MTX enabled us to compare the protonation states of histidine imidazole rings.Our results demonstrate the usefulness of His-HDX-MS in probing the microenvironments of histidine residues within proteins

Identification of children who may benefit from self-hypnosis at a pediatric pulmonary center

BACKGROUND: Emotional difficulties can trigger respiratory symptoms. Thus, children presenting with respiratory complaints may benefit from a psychological intervention. The purpose of this study was to define the proportion of patients referred to a Pediatric Pulmonary Center who may benefit from instruction in self-hypnosis, as a psychological intervention. METHODS: A retrospective chart review was conducted for all newly referred patients to the SUNY Upstate Medical University Pediatric Pulmonary Center during an 18 month period beginning January 1, 2000. Patients were offered hypnosis if they presented with symptoms or signs suggestive of psychological difficulties. Hypnosis was taught in one or two 15–45 minute sessions by a pediatric pulmonologist. RESULTS: Of 725 new referrals, 424 were 0–5 years old, 193 were 6–11 years old, and 108 were 12–18 years old. Diagnoses of anxiety, habit cough, or vocal cord dysfunction accounted for 1% of the 0–5 year olds, 20% of the 6–11 year olds, and 31% of the 12–18 year olds. Hypnotherapy was offered to 1% of 0–5 year olds, 36% of 6–11 year olds, and 55% of 12–18 year olds. Of 81 patients who received instruction in self-hypnosis for anxiety, cough, chest pain, dyspnea, or inspiratory difficulties, 75% returned for follow-up, and among the returning patients 95% reported improvement or resolution of their symptoms. CONCLUSION: A large number of patients referred to a Pediatric Pulmonary Center appeared to benefit from instruction in self-hypnosis, which can be taught easily as a psychological intervention

Study protocol: evaluation of a parenting and stress management programme: a randomised controlled trial of Triple P discussion groups and stress control

&lt;br&gt;Background: Children displaying psychosocial problems are at an increased risk of negative developmental outcomes. Parenting practices are closely linked with child development and behaviour, and parenting programmes have been recommended in the treatment of child psychosocial problems. However, parental mental health also needs to be addressed when delivering parenting programmes as it is linked with parenting practices, child outcomes, and treatment outcomes of parenting programmes. This paper describes the protocol of a study examining the effects of a combined intervention of a parenting programme and a cognitive behavioural intervention for mental health problems.&lt;/br&gt; &lt;br&gt;Methods: The effects of a combined intervention of Triple P Discussion Groups and Stress Control will be examined using a randomised controlled trial design. Parents with a child aged 3?8?years will be recruited to take part in the study. After obtaining informed consent and pre-intervention measures, participants will be randomly assigned to either an intervention or a waitlist condition. The two primary outcomes for this study are change in dysfunctional/ineffective parenting practices and change in symptoms of depression, anxiety, and stress. Secondary outcomes are child behaviour problems, parenting experiences, parental self-efficacy, family relationships, and positive parental mental health. Demographic information, participant satisfaction with the intervention, and treatment fidelity data will also be collected. Data will be collected at pre-intervention, mid-intervention, post-intervention, and 3-month follow-up.&lt;/br&gt; &lt;br&gt;Discussion: The aim of this paper is to describe the study protocol of a randomised controlled trial evaluating the effects of a combined intervention of Triple P Discussion Groups and Stress Control in comparison to a waitlist condition. This study is important because it will provide evidence about the effects of this combined intervention for parents with 3?8?year old children. The results of the study could be used to inform policy about parenting support and support for parents with mental health problems. Trial registration ClinicalTrial.gov: NCT01777724, UTN: U1111-1137-1053.&lt;/br&gt

Towards a Linked democracy model

In this chapter we lay out the properties of participatory ecosystems as linked democracy ecosystems. The goal is to provide a conceptual roadmap that helps us to ground the theoretical foundations for a meso-level, institutional theory of democracy. The identification of the basic properties of a linked democracy eco-system draws from different empirical examples that, to some extent, exhibit some of these properties. We then correlate these properties with Ostrom's design principles for the management of common-pool resources (as generalised to groups cooperating and coordinating to achieve shared goals) to open up the question of how linked democracy ecosystems can be governed