Electrochemically Generated Luminescence of Luminol and Luciferin in Ionic Liquids

Electrochemiluminescence (ECL) is the generation of light triggered by an electrochemical reaction. ECL has been extensively studied in solvent-based electrolytes, but there is a lack of data on using electrode reactions to populate an excited-state light emitter in room temperature ionic liquids (RTILs). This work explores the current response, light intensity (photon counting), and spectral signatures of the cathodic ECL of luminol and firefly's luciferin in imidazolium-based RTILs. We have demonstrated that the cathodic (superoxide-triggered) ECL of both luminol and adenylate-ester of firefly's luciferin is viable in RTILs, explored the effect of water contaminations, and importantly, shown that the ECL signal persists for up to about 700 s after the removal of the external cathodic pulse, which is probably due to the stabilization of superoxide by double-layer cation-rich structures. Long-lived RTIL double-layer structures and their endogenous fields are detected as stable and discrete open-circuit potential plateaus

Not All Children with Under-Control Asthma are Controlled

Subclinical lung function alterations can sometimes be discovered in asthmatic patients under clinical control. This study aimed to identify the burden of asthmatic children with subclinical airways abnormalities who may benefit from an adjustment in asthma therapy. 134 6-to-17-year-old asthmatic children were enrolled. Of them, 98 presented apparently under clinical control disease and all performed spirometry before and after bronchodilation: 17 (17.3%) had a positive bronchodilation test, in addition to significantly lower lung function indexes as compared to those with under-control asthma who had a negative bronchodilation test. These patients were randomized and re-evaluated: patients (n=8) receiving an adjustment in their therapy showed an improvement in lung function tests and quality of life indexes as compared to 7 without therapy adjustment. In conclusion, a substantial number of apparently-under-control asthmatic children show airways alterations that can be improved by adjusting their therapy, which also seems to enhance their quality of life

Separating Convective from Diffusive Mass Transport Mechanisms in Ionic Liquids by Redox Pro-fluorescence Microscopy

The study of electrochemical reactivity requires analytical techniques capable of probing the diffusion of reactants and products to and from electrified interfaces. Information on diffusion coefficients is often obtained indirectly by modeling current transients and cyclic voltammetry data, but such measurements lack spatial resolution and are accurate only if mass transport by convection is negligible. Detecting and accounting for adventitious convection in viscous and wet solvents, such as ionic liquids, is technically challenging. We have developed a direct, spatiotemporally resolved optical tracking of diffusion fronts which can detect and resolve convective disturbances to linear diffusion. By tracking the movement of an electrode-generated fluorophore, we demonstrate that parasitic gas evolving reactions lead to 10-fold overestimates of macroscopic diffusion coefficients. A hypothesis is put forward linking large barriers to inner-sphere redox reactions, such as hydrogen gas evolution, to the formation of cation-rich overscreening and crowding double layer structures in imidazolium-based ionic liquids

Features, risk factors and clinical outcome of {"}very late{"} recurrences after surgery for localized renal carcinoma: A retrospective evaluation of a cohort with a minimum of 10 years of follow up

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A Lithium Experiment in the Program of Solar Neutrino Research

The experiments sensitive to pp-neutrinos from the Sun are very perspective for the precise measurement of a mixing angle $\theta_{12}$. A $\nu$e$^{-}$ scattering experiment (Xmass) and/or a charged-current experiment (the indium detector) can measure the flux of electron pp-neutrinos. One can find the total flux of pp-neutrinos from a luminosity constraint after the contribution of $^7$Be and CNO neutrinos to the total luminosity of the Sun are measured. The radiochemical experiment utilizing a lithium target has the high sensitivity to the CNO neutrinos, thus, it has a good promise for the precise measurement of a mixing angle and for the test of a current theory of the evolution of the stars.Comment: 6 pages, 2 figures, 1 table, A report made by A.Kopylov at International Conference NANP-2005, June 2005, Dubna, Russi

Extended Formulations in Mixed-integer Convex Programming

We present a unifying framework for generating extended formulations for the polyhedral outer approximations used in algorithms for mixed-integer convex programming (MICP). Extended formulations lead to fewer iterations of outer approximation algorithms and generally faster solution times. First, we observe that all MICP instances from the MINLPLIB2 benchmark library are conic representable with standard symmetric and nonsymmetric cones. Conic reformulations are shown to be effective extended formulations themselves because they encode separability structure. For mixed-integer conic-representable problems, we provide the first outer approximation algorithm with finite-time convergence guarantees, opening a path for the use of conic solvers for continuous relaxations. We then connect the popular modeling framework of disciplined convex programming (DCP) to the existence of extended formulations independent of conic representability. We present evidence that our approach can yield significant gains in practice, with the solution of a number of open instances from the MINLPLIB2 benchmark library.Comment: To be presented at IPCO 201

Antimicrobial Stewardship Interventions in Pediatric Oncology: A Systematic Review

Antimicrobial stewardship programs represent efficacious measures for reducing antibiotic overuse and improving outcomes in different settings. Specific data on pediatric oncology are lacking. We conducted a systematic review on the PubMed and Trip databases according to the PRISMA guidelines, searching for reports regarding antimicrobial stewardship in pediatric oncology and hematology patients. The aim of the study was to summarize the present literature regarding the implementation of antimicrobial stewardship programs or initiatives in this particular population, and provide insights for future investigations. Nine papers were included in the qualitative analysis: three regarding antifungal interventions, five regarding antibacterial interventions, and one regarding both antifungal and antibacterial stewardship interventions. Variable strategies were reported among the included studies. Different parameters were used to evaluate the impact of these interventions, including days of therapy per 1000-patient-days, infections with resistant strains, safety analysis, and costs. We generally observed a reduction in the prescription of broad-spectrum antibiotics and an improved appropriateness, with reduced antibiotic-related side effects and no difference in infection-related mortality. Antibiotic stewardship programs or interventions are effective in reducing antibiotic consumption and improving outcomes in pediatric oncology hematology settings, although stewardship strategies differ substantially in different institutions. A standardized approach needs to be implemented in future studies in order to better elucidate the impact of stewardship programs in this category of patients

Luciferase-free Luciferin Electrochemiluminescence

Luciferin is one of Nature's most widespread luminophores, and enzymes that catalyze luciferin luminescence are the basis of successful commercial “glow” assays for gene expression and metabolic ATP formation. Herein we report an electrochemical method to promote firefly's luciferin luminescence in the absence of its natural biocatalyst—luciferase. We have gained experimental and computational insights on the mechanism of the enzyme-free luciferin electrochemiluminescence, demonstrated its spectral tuning from green to red by means of electrolyte engineering, proven that the colour change does not require, as still debated, a keto/enol isomerization of the light emitter, and gained evidence of the electrostatic-assisted stabilization of the charge-transfer excited state by double layer electric fields. Luciferin's electrochemiluminescence, as well as the in situ generation of fluorescent oxyluciferin, are applied towards an optical measurement of diffusion coefficients

In‐Depth Immunological Typization of Children with Sickle Cell Disease: A Preliminary Insight into Its Plausible Correlation with Clinical Course and Hydroxyurea Therapy

Sickle cell disease (SCD) is a condition of functional hypo‐/a‐splenism in which predisposition to bacterial infections is only a facet of a wide spectrum of immune‐dysregulation disorders forming the clinical expression of a peculiar immunophenotype. The objective of this study was to perform an in‐depth immunophenotypical characterization of SCD pediatric patients, looking for plausible correlations between immunological biomarkers, the impact of hydroxyurea (HU) treatment and clinical course. This was an observational case–control study including 43 patients. The cohort was divided into two main groups, SCD subjects (19/43) and controls (24/43), differing in the presence/absence of an SCD diagnosis. The SCD group was split up into HU+ (12/19) and HU− (7/19) subgroups, respectively receiving or not a concomitant HU treatment. The principal outcomes measured were differences in the immunophenotyping between SCD patients and controls through chi‐squared tests, t‐tests, and Pearson’s correlation analysis between clinical and immunological parameters. Leukocyte and neutrophil increase, T‐cell depletion with prevalence of memory T‐cell compartment, NK and B‐naïve subset elevation with memory and CD21low B subset reduction, and IgG expansion, significantly distinguished the SCD HU− subgroup from controls, with naïve T cells, switched‐memory B cells and IgG maintaining differences between the SCD HU+ group and controls (p‐value of <0.05). The mean CD4+ central‐memory T‐cell% count was the single independent variable showing a positive correlation with vaso‐occlusive crisis score in the SCD group (Pearson’s R = 0.039). We report preliminary data assessing plausible clinical implications of baseline and HU‐related SCD immunophenotypical alterations, which need to be validated in larger samples, but potentially affecting hypo‐/a‐splenism immuno‐chemoprophylactic recommendations

Branch and bound based coordinate search filter algorithm for nonsmooth nonconvex mixed-integer nonlinear programming problems

Publicado em "Computational science and its applications – ICCSA 2014...", ISBN 978-3-319-09128-0. Series "Lecture notes in computer science", ISSN 0302-9743, vol. 8580.A mixed-integer nonlinear programming problem (MINLP) is a problem with continuous and integer variables and at least, one nonlinear function. This kind of problem appears in a wide range of real applications and is very difficult to solve. The difficulties are due to the nonlinearities of the functions in the problem and the integrality restrictions on some variables. When they are nonconvex then they are the most difficult to solve above all. We present a methodology to solve nonsmooth nonconvex MINLP problems based on a branch and bound paradigm and a stochastic strategy. To solve the relaxed subproblems at each node of the branch and bound tree search, an algorithm based on a multistart strategy with a coordinate search filter methodology is implemented. The produced numerical results show the robustness of the proposed methodology.This work has been supported by FCT (Fundação para a Ciência e aTecnologia) in the scope of the projects: PEst-OE/MAT/UI0013/2014 and PEst-OE/EEI/UI0319/2014