Simultaneous Heavy Metal-Polycyclic Aromatic Hydrocarbon Removal by Native Tunisian Fungal Species

Multi-contamination by organic pollutants and toxicmetals is common in anthropogenic and industrial environments. In this study, the five fungal strains Chaetomium jodhpurense (MH667651.1), Chaetomium maderasense (MH665977.1), Paraconiothyrium variabile (MH667653.1), Emmia lacerata, and Phoma betae (MH667655.1), previously isolated in Tunisia, were investigated for the simultaneous removal and detoxification of phenanthrene (PHE) and benzo[a]anthracene (BAA), as well as heavy metals (HMs) (Cu, Zn, Pb and Ag) in Kirk’s media. The removal was analysed using HPLC, ultra-high performance liquid chromatography (UHPLC) coupled to a QToF mass spectrometer, transmission electron microscopy, and toxicology was assessed using phytotoxicity (Lepidium sativum seeds) and Microtox® (Allivibrio fisherii) assays. The PHE and BAA degradation rates, in free HMs cultures, reached 78.8% and 70.7%, respectively. However, the addition of HMs considerably affected the BAA degradation rate. The highest degradation rates were associated with the significant production of manganese-peroxidase, lignin peroxidase, and unspecific peroxygenase. The Zn and Cu removal efficacy was considerably higher with live cells than dead cells. Transmission electron microscopy confirmed the involvement of both bioaccumulation and biosorption processes in fungal HM removal. The environmental toxicological assays proved that simultaneous PAH and HM removal was accompanied by detoxification. The metabolites produced during co-treatment were not toxic for plant tissues, and the acute toxicity was reduced. The obtained results indicate that the tested fungi can be applied in the remediation of sites simultaneously contaminated with PAHs and HMs.Ministry of Higher Education and Scientific Research in TunisiaFEDER/Junta de Andalucía-Consejería de TransformaciónEconómica, Industria, Conocimiento y Universidades (B-RNM-204-UGR20)Secretaria de Investigacion y posgrado SIP of IPN (Project number 20230427

Palladium-catalyzed Suzuki–Miyaura cross-coupling with α\alpha -aminophosphonates based on 1,3,4-oxadiazole as ligands

The synthesis of a palladium complex bearing two diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-nitrophenyl)methyl]phosphonates as ligands has demonstrated the ability of this type of $\alpha$-aminophosphonates to coordinate to the palladium(II) ion via their electronically enriched nitrogen atom of the 1,3,4-oxadiazole ring. The complex was fully characterized by elemental analysis, infrared, NMR and mass spectrometry. A solid-state structure revealed the trans coordination of the two nitrogenated ligands. The presence of a hemilabile P(O)(OEt)$_{2}$ moiety in the $\alpha$-aminophosphonates was exploited into palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl halides. The formation of ($N{,}O$)-chelate intermediates may increase the steric hindrance and the electronic density of the metal, which should favor the oxidative addition and the reductive elimination/product decoordination elementary steps. With our catalytic systems, good activities for the formation of ortho-di/trisubstituted biphenyl compounds were observed from aryl bromides using only 0.5 mol% of palladium. Cross-coupling of aryl chlorides required a catalyst loading of 1 mol% to generate ortho-substituted biphenyls

Palladium-catalyzed Suzuki–Miyaura cross-coupling with α\alpha -aminophosphonates based on 1,3,4-oxadiazole as ligands

The synthesis of a palladium complex bearing two diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-nitrophenyl)methyl]phosphonates as ligands has demonstrated the ability of this type of $\alpha$-aminophosphonates to coordinate to the palladium(II) ion via their electronically enriched nitrogen atom of the 1,3,4-oxadiazole ring. The complex was fully characterized by elemental analysis, infrared, NMR and mass spectrometry. A solid-state structure revealed the trans coordination of the two nitrogenated ligands. The presence of a hemilabile P(O)(OEt)$_{2}$ moiety in the $\alpha$-aminophosphonates was exploited into palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl halides. The formation of ($N{,}O$)-chelate intermediates may increase the steric hindrance and the electronic density of the metal, which should favor the oxidative addition and the reductive elimination/product decoordination elementary steps. With our catalytic systems, good activities for the formation of ortho-di/trisubstituted biphenyl compounds were observed from aryl bromides using only 0.5 mol% of palladium. Cross-coupling of aryl chlorides required a catalyst loading of 1 mol% to generate ortho-substituted biphenyls

Time-varying relationship between conventional and unconventional monetary policies and risk aversion : international evidence from time- and frequency-domains

This paper analyzes the time-varying relationship between risk aversion and both conventional and unconventional monetary policy in an international context and at different frequencies using a wavelet coherency analysis. Our main results suggest the existence of a dynamic relationship between the two variables depending on timescales and on the periods. Thus, a short-run negative relationship leading from the risk aversion variable to the monetary policy measure is found for most of the period, suggesting that monetary policy reacts more aggressively in periods of high risk aversion. Furthermore, during the financial crisis, we find a long-run negative relationship leading from the monetary policy to the risk aversion index, suggesting that a lax monetary policy could lead to financial instability. US monetary policy has also significant effects on the risk aversion rates in the Euro Area, Japan and the UK.The Ministerio de Economía y Competitividad (ECO2017-83183-R).http://link.springer.com/journal/1812022-01-18hj2021Economic

The relationship between monetary policy and uncertainty in advanced economies : evidence from time- and frequency-domains

In this work we offer new insight into the relationship between interest rates and uncertainty for several advanced economies (Canada, Euro Area, Japan, UK, US) for the period 2003−2018. For this purpose, we utilize wavelets, which allow us to analyze how the relationship changes over time and across different frequencies, and to make inference about causality. We also use the daily shadow interest rate measure of Krippner (2012), (2013) to capture the stance of monetary policy making at the zero lower bound, and the uncertainty measure by Scotti (2016) to measure uncertainty related to the real economy. Our findings suggest that there is significant co-movement over time and across different frequencies in all the countries we analyze. Corresponding to the similar, yet different conduct of monetary policy, we also find that the relationship exhibits different characteristics and causality in all the economies we analyze, implying that one must be careful not to draw generalized conclusions.http://www.elsevier.com/locate/qrefhj2021Economic

Semantic and Contextual Knowledge Representation for Lexical Disambiguation: Case of Arabic-French Query Translation

We present in this paper, an automatic query translation system in cross-language information retrieval (Arabic-French). For the lexical disambiguation, our system combines between two resources: a bilingual dictionary and a parallel corpus. To select the best translation, our method is based on a correspondence measure between two semantic networks. The first one represents the senses of ambiguous terms of the query. The second one is a semantic network contextually enriched, representing the collection of sentences responding to the query. This collection forms the knowledge base of our disambiguation method and it is obtained by alignment with the relevant sentences in Arabic. The evaluation of the proposed system shows the advantage of the contextual enrichment on the quality of the translation. We obtained a high precision, relatively proportional to the precision provided by the used alignment. Finally, our translation demonstrates its potential by comparing its Bleu score with that of Google translate.</p

Optical properties of biosynthesized nanoscaled Eu2O3 for red luminescence applications

This contribution reports on the optical properties of biosynthesised Eu2O3 nanoparticles bioengineered for the first time by a green and cost effective method using aqueous fruit extracts of Hyphaene thebaica as an effective chelating and capping agent. The morphological, structural, and optical properties of the samples annealed at 500°C were confirmed by using a high-resolution transmission electron microscope (HR-TEM), x-ray diffraction analysis (XRD), UV–Vis spectrocopy, and photoluminescence spectrometer. The XRD results confirmed the characteristic body-centered cubic (bcc) structure of Eu2O3 nanoparticles with an average size of 20 nm. HR-TEM revealed square type morphology with an average size of ∼6nm. Electron dispersion energy dispersive x-ray spectroscopy spectrum confirmed the elemental single phase nature of pure Eu2O3. Furthuremore, the Fourier transformed infrared spectroscopy revealed the intrinsic characteristic peaks of Eu−O bond stretching vibrations. UV–Vis reflectance proved that Eu2O3 absorbs in a wide range of the solar spectrum from the VUV–UV region with a bandgap of 5.1 eV. The luminescence properties of such cubic structures were characterized by an intense red emission centered at 614 nm. It was observed that the biosynthesized Eu2O3 nanoparticles exhibit an efficient red-luminescence and hence a potential material as red phosphor

Степлерна гемороїдектомія при комбінованому геморої III–IV стадії, в поєднанні з хронічною анальною тріщиною

The aim of the work: to compare early results of stapler circular hemorrhoidectomy and hemorrhoidectomy according to Milligan- Morgan in chronic combined hemorrhoids III-IV stage complicated by chronic anal fissure.Materials and Methods. All patients in the preoperative period underwent clinical and biochemical studies of blood and urine, ultra­sound examination of the abdominal cavity, consultation of an infectionist, oncologist. All patients have instrumental studies of the rectum and colon to exclude other pathology.Results and Discussion. In the work the comparative analysis of early results of surgical treatment of chronic hemorrhoids III-IV stage complicated by a chronic anal fissure was presented: 27 (55.1 %) patients in the first group underwent stapler hemorrhoidectomy ac­cording to the method we developed, excision of the anal fissure by a laser, 22 (44.9 %) of patients in the second group suffered hemor­rhoidectomy by Milligan-Morgan in the second modification of the Institute of Proctology of Moscow, excision of the anal fissure by a laser. In the early postoperative period (up to 10 days) evaluated: the duration of the operation; Pain intensity at the 10-point visual analog scale after 24, 120 and 240 hours after surgery; duration of pain syndrome; return time to normal activity; the frequency of early (up to 30 days) postoperative complications. It was found that return to normal activity in the second group lasted 1.6 times longer than in the first one; early results in the first group were better th an in the second.Цель работы: сравнить ранние результаты степлерной циркулярной геморроидэктомии и геморроидэктомии по Миллиган– Морганом при хроническом комбинированном геморрое III–IV стадии в сочетании с хронической анальной трещиной.Материалы и методы. Всем пациентам в предоперационном периоде проведены клинические и биохимические исследования крови и мочи, ультразвуковое исследование органов брюшной полости, консультации инфекциониста, онколога. Всем пациентам проведены инструментальные исследования прямой и ободочной кишки для исключения другой патологии.Результаты исследований и их обсуждение. В работе представлен сравнительный анализ ранних результатов хирургического лечения хронического геморроя III–IV стадии в сочетании с хронической анальной трещиной: 27 (55,1 %) больным первой группы было выполнено степлерные геморроидэктомия согласно разработанному нами способом, иссечение анальной трещины лазером, 22 (44, 9 %) больных второй группы перенесли геморроидэктомия по Миллиганом-Морганом во второй модификации НИИ проктологии м. Москвы, иссечение анальной трещины лазером. В ранний послеоперационный период (до 10 суток) оценивали: продолжительность операции; интенсивность боли по 10-бальной визуальной аналоговой шкале через 24, 120 и 240 ч после операции; продолжительность болевого синдрома; время возвращения к нормальной активности; частоту ранних (до 30 суток) послеоперационных осложнений. Установлено, что возвращение к нормальной активности во второй группе продолжалось в среднем в 1,6 раза дольше, чем в первой; ранние результаты в первой группе были лучше, чем во второй.Мета роботи: порівняти ранні результати степлерної циркулярної гемороїдектомії та гемороїдектомії за Мілліган–Морганом при хронічному комбінованому геморої III–IV стадії, в поєднанні з хронічною анальною тріщиною.Матеріали і методи. Всім пацієнтам у передопераційний період проведено клінічні та біохімічні дослідження крові та сечі, ультразвукове дослідження органів черевної порожнини, консультації інфекціоніста, онколога. Всім пацієнтам проведено інструментальні дослідження прямої та ободової кишки для виключення іншої патології.Результати досліджень та їх обговорення. У роботі представлено порівняльний аналіз ранніх результатів хірургічного лікування хронічного геморою III–IV стадії, в поєднанні з хронічною анальною тріщиною: 27 (55,1%) хворим першої групи було виконано степлерну гемороїдектоміюзгідно з розробленим нами способом, висікання анальної тріщини лазером, 22 (44,9 %) хворі другої групи перенесли гемороїдектомію за Мілліганом–Морганом в другій модифікації НДІ проктології м. Москви, висікання анальної тріщини лазером.У ранній післяопераційний період (до 10 діб) оцінювали: тривалість операції; інтенсивність болю за 10-бальною візуальною аналоговою шкалою через 24, 120 і 240 год після операції; тривалість больового синдрому; час повернення до нормальної активності; частоту ранніх (до 30 діб) післяопераційних ускладнень. Встановлено, що повернення до нормальної активності в другій групі тривало в середньому в 1,6 раза довше, ніж в першій; ранні результати в першій групі були кращими, ніж в другій

Electrodeposition of 4,4′-di-tert-butylbiphenyl peroxide from the anodic oxidation of p-tert-butylphenol in an alkaline acetonitrile solution

The electrogeneration of pure 4,4′-di-tert-butylbiphenyl peroxide as an electrodeposit could be achieved on a platinum electrode through the anodic oxidation of p-tert butylphenol in the presence of Lutidine, in addition to several soluble oligomers. The electrochemical and theoretical studies have shown that the favored coupling reaction corresponds to the O–O bond, albeit it is generally being considered unstable. Without the strong base, a mixture of trimer, tetramer and pentamer was deposited. The peroxide product presents a different electroactivity to that of the phenolic compound, with the appearance of a redox process involving cathodic and anodic symmetrical peaks at −0.10/0.15 V versus SCE, which indicates the preference of the polymer to adhere onto the electrode surface. The thermal degradation has also been analyzed. Quantum-chemical calculations reveal the reason for the oxygen–oxygen coupling.The authors would like to thank the Tunisian Ministry of Higher Education and Research for its financial support as well as the King Saud University for its funding through the Research Group Project No RGP-VPP-243. They would also like to thank the Spanish Ministry of Economy and Competitiveness for its financial support and the STIs for the ERDF funds (MAT2013-42007-P) and the Generalitat Valenciana (PROMETEO2013/ 038)