Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

Toksikološke metode otkrivanja opojnih droga u tragovima: kromatografska, spektroskopska i biološka karakterizacija derivata ecstasyja

Analysis often reveals variability in the composition of ecstasy pills from pure 3,4-methylenedioxymethamphetamine (MDMA) to mixtures of MDMA derivatives, amphetamine, and other unidentifi ed substances. For a comprehensive toxicological analysis one needs to know all steps to MDMA synthesis which may originate impurities. The aim of this study was to synthesise and determine the chemical-physical and in vitro biological properties of a series of MDMA derivatives. 3,4-methylendioxyphenyl-2-nitropropene (MDNP) was obtained by condensation of piperonal with an excess of nitroethane in the presence of ammonium acetate. MDNP was then reduced to methylenedioxyamphetamine (MDA) by LiAlH3. All compounds were analysed using HPLC and spectroscopic technique [Raman, nuclear magnetic resonance (NMR), or infrared (IR)] at all the steps of synthesis. In addition, we assessed the biological potentials of these compounds by measuring in vitro their (i) blood cell/whole blood partition coeffi cient, (ii) binding to plasmatic proteins (Fbp), and (iii) membrane adsorption. Chemical structure was determined with antibody fl uorescence polarisation immunoassay (FPIA). This study showed the presence of solid impurities, particularly of a neurotoxic compound of Al3+ in the fi nal products. FPIA identifi ed the aminoethane group close to the substituted benzene ring, but did not detect the two major precursors of MDMA: MDNP and piperonal. Raman spectroscopy is an attractive alternative technique to characterise ecstasy pills and it can identify stereoisomeric forms such as cis-MDNP and trans-MDNP, which exhibit signals at 1650 cm-1 and 1300 cm-1, respectively.Analize često otkriju neujednačenost sastava tableta ecstasyja od čistoga 3,4-metilendioksimetamfetamina (MDMA) do mješavina njegovih derivata, amfetamina i drugih neutvrđenih tvari. Stoga je za kvalitetnu toksikološku analizu potreban uvid u sve korake sinteze MDMA, s obzirom na to da se ondje vjerojatno kriju izvori nečistoće (prekursori, katalizatori). Cilj ovog ispitivanja bio je sintetizirati derivate MDMA te napraviti njihovu kemijsko-fi zikalnu i biološku in vitro karakterizaciju. 3,4-metilendioksifenil-2-nitropropen (MDNP) dobiven je kondenzacijom piperonala u suvišku nitroetana uz dodatak amonijeva acetata. Njegovom redukcijom s pomoću LiAlH3 dobiven je 3,4-metilendioksiamfetamin (MDA). Svi spojevi iz pojedinih koraka sinteze karakterizirani su s pomoću tekućinske kromatografi je visoke djelotvornosti (HPLC) i spektroskopskih tehnika [Ramanove spektroskopije, nuklearne magnetske rezonancije (NMR-a) te infracrvene spektroskopije (IR-a)]. Usto je ocijenjen i njihov biološki učinak in vitro mjerenjem (i) koefi cijenta raspodjele krvna stanica/puna krv, (ii) vezanja za bjelančevine u plazmi (Fbp) te (iii) adsorpcije na membranu. Kemijska je struktura utvrđena s pomoću fl uorescentnoga polarizacijskog imunokemijskog testa (FPIA). Analiza je u konačnim proizvodima utvrdila prisutnost krutih nečistoća, napose spojeva neurotoksičnog aluminija (Al3+). FPIA je prepoznao aminoetansku skupinu blizu supstituiranoga benzenskog prstena, ali ne i dva glavna prekursora za MDMA: MDNP i piperonal. Posebno je zanimljiva Ramanova spektroskopija budući da (i) pruža privlačnu alternativu za karakterizaciju sastava tableta ecstasyja te (ii) može otkriti stereoizomerne cis/trans-oblike spoja poput cis-MDNP-a odnosno trans-MDNP-a, čiji se signal vidi na 1650 cm-1 odnosno 1300 cm-1

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO2 anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm−3 were carried out on a Ta/PbO2 anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm−3). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%

A comparison of electrochemical degradation of phenol on boron doped diamond and lead dioxide anodes

This work compares two electrode materials used to mineralize phenol contained in waste waters. Two disks covered with either boron doped diamond (BDD) or PbO2 were used as anodes in a one compartment flow cell under the same hydrodynamic conditions. Efficiencies of galvanostatic electrolyses are compared on the basis of measurements of Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD). Galvanostatic electrolyses were monitored by analysis of phenol and of its oxidation derivatives to evaluate the operating time needed for complete elimination of toxic aromatics. The experimental current efficiency is close to the theoretical value for the BDD electrode. Other parameters being equal, phenol species disappeared at the same rate using the two electrode materials but the BDD anode showed better efficiency to eliminate TOC and COD. Moreover, during the electrolysis less intermediates are formed with BDD compared to PbO2 whatever the current density. A comparison of energy consumption is given based on the criterion of 99% removal of aromatic compounds

Prediction of High-Grade Vesicoureteral Reflux after Pediatric Urinary Tract Infection: External Validation Study of Procalcitonin-Based Decision Rule

BACKGROUND: Predicting vesico-ureteral reflux (VUR) 653 at the time of the first urinary tract infection (UTI) would make it possible to restrict cystography to high-risk children. We previously derived the following clinical decision rule for that purpose: cystography should be performed in cases with ureteral dilation and a serum procalcitonin level 650.17 ng/mL, or without ureteral dilatation when the serum procalcitonin level 650.63 ng/mL. The rule yielded a 86% sensitivity with a 46% specificity. We aimed to test its reproducibility. STUDY DESIGN: A secondary analysis of prospective series of children with a first UTI. The rule was applied, and predictive ability was calculated. RESULTS: The study included 413 patients (157 boys, VUR 653 in 11%) from eight centers in five countries. The rule offered a 46% specificity (95% CI, 41-52), not different from the one in the derivation study. However, the sensitivity significantly decreased to 64% (95%CI, 50-76), leading to a difference of 20% (95%CI, 17-36). In all, 16 (34%) patients among the 47 with VUR 653 were misdiagnosed by the rule. This lack of reproducibility might result primarily from a difference between derivation and validation populations regarding inflammatory parameters (CRP, PCT); the validation set samples may have been collected earlier than for the derivation one. CONCLUSIONS: The rule built to predict VUR 653 had a stable specificity (ie. 46%), but a decreased sensitivity (ie. 64%) because of the time variability of PCT measurement. Some refinement may be warranted

Pediatric T- and NK-cell lymphomas: new biologic insights and treatment strategies

T- and natural killer (NK)-cell lymphomas are challenging childhood neoplasms. These cancers have varying presentations, vast molecular heterogeneity, and several are quite unusual in the West, creating diagnostic challenges. Over 20 distinct T- and NK-cell neoplasms are recognized by the 2008 World Health Organization classification, demonstrating the diversity and potential complexity of these cases. In pediatric populations, selection of optimal therapy poses an additional quandary, as most of these malignancies have not been studied in large randomized clinical trials. Despite their rarity, exciting molecular discoveries are yielding insights into these clinicopathologic entities, improving the accuracy of our diagnoses of these cancers, and expanding our ability to effectively treat them, including the use of new targeted therapies. Here, we summarize this fascinating group of lymphomas, with particular attention to the three most common subtypes: T-lymphoblastic lymphoma, anaplastic large cell lymphoma, and peripheral T-cell lymphoma-not otherwise specified. We highlight recent findings regarding their molecular etiologies, new biologic markers, and cutting-edge therapeutic strategies applied to this intriguing class of neoplasms

Thoracic Epidural Analgesia And Survival In Acute Pancreatitis: A Multicenter Propensity Analysis

International Conference of the American-Thoracic-Society (ATS), Washington, DC, MAY 19-24, 2017International audienc