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The electrocatalytic properties of Ru complexes are of great technological interest given their potential application in reactions such water splitting and CO2 reduction. In this work, a novel terpyridine-based Ru(II) complex, [RuCl(trpy)(acpy)], trpy = 2,2':6',2''-terpyridine, acpy- = 2-pyridylacetate was synthesized and its spectroscopic, electrochemical and catalytic properties were explored in detail. In dry acetonitrile, the complex exhibits two reduction peaks at -1.95 V and -2.20 V vs. Fc/Fc+, attributed to consecutive 1 e- reduction. Under CO2 atmosphere, a catalytic wave is observed (Eonset = 2.1 V vs. Fc/Fc+), with CO as the main reduction product. Bulk electrolysis reveals a turnover number (TON) of 12 (kobs = 1.5 s-1). In the presence of 1% water, an improvement in the catalytic activity is observed (TONCO = 21 and kobs = 2.0 s-1) and, additionally, formate was also detected (TONHCOO = 7). Spectroelectrochemical experiments allowed the identification of a metallocarboxylate (Ru-COO-) intermediate under anhydrous conditions, while in water, the partial labilization of the acpy- ligand was observed in the course of the catalytic cycle. The experimental data was combined with DFT calculations, allowing the proposal of a catalytic cycle. The results establish important relationships between selectivity, ligand structure and reaction conditions.

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Considering our previous findings on the remarkable activity exhibited by cobalt(III) with 2-acetylpyridine-N(4)-R-thiosemicarbazone (Hatc-R) compounds against Mycobacterium tuberculosis, the present study aimed to explored new structure features of the complexes of the type [Co(atc--R)2]Cl, where R = methyl (Me, 1) or phenyl (Ph, 2) (13C NMR, high-resolution mass spectrometry, LC-MS/MS, fragmentation study) together with its antibacterial and antiviral biological activities. The minimal inhibitory and minimal bactericidal concentrations (MIC and MBC) were determined, as well as the antiviral potential of the complexes on chikungunya virus (CHIKV) infection in vitro and cell viability. [Co(atc-Ph)2]Cl revealed promising MIC and MBC values which ranged from 0.39 to 0.78 µg/mL in two strains tested and presented high potential against CHIKV by reducing viral replication by up to 80%. The results showed that the biological activity is strongly influenced by the peripheral substituent groups at the N(4) position of the atc-R1- ligands. In addition, molecular docking analysis was performed. The relative binding energy of the docked compound with five bacteria strains was found in the range of -3.45 and -9.55 kcal/mol. Thus, this work highlights the good potential of cobalt(III) complexes and provide support for future studies on this molecule aiming at its antibacterial and antiviral therapeutic application.

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[PtCl2(phen)] reacts with thiosemicarbazones derived from ß-diketones (H2LR) leading to an intramolecular C-C coupling between phen and the ketone upon formation of tetradentate N,N,N,S chelates [PtII(LRphen)]. The reactions proceed via bidentate coordination of the doubly deprotonated (LR)2- followed by an intra-nucleophilic attack and consecutive C-C bond formation.

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Leishmaniasis, a neglected tropical disease caused by protozoans of the genus Leishmania, kills around 20-30 thousand people in Africa, Asia, and Latin America annually and, despite its potential lethality, it can be treated and eventually cured. However, the current treatments are limited owing to severe side effects and resistance development by some Leishmania. These factors make it urgent to develop new leishmanicidal drugs. In the present study, three ruthenium(II) organometallic complexes containing as ligands the commercially available anti-inflammatories diclofenac (dic), ibuprofen (ibu), and naproxen (nap) were synthesized, characterized, and subjected to in vitro leishmanicidal activity. The in vitro cytotoxicity assays against Leishmania (L.) amazonensis and Leishmania (L.) infantum promastigotes have shown that complexes [RuCl(dic)(η6-p-cymene)] (1) and [RuCl(nap)(η6-p-cymene)] (3) were active against both Leishmania species. Complex [RuCl(ibu)(η6-p-cymene)] (2) has exhibited no activity. The IC50 values for the two active complexes were respectively 7.42 and 23.55 µM, for L. (L.) amazonensis, and 8.57 and 42.25 µM, for L. (L.) infantum. Based on the toxicological results and computational analysis, we proposed a correlation between the complexes and their activity. Our results suggest both complexation to ruthenium(II) and ligands structure are key elements to leishmanicidal activity.

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Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe2+, Fe3+ and Fe3+-citrate and Fe3+-oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C17H19FN3O4, m/z 348; C17H21FN3O5, m/z 366; and C13H12FN2O3, m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C17H21FN3O5, m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions.

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The feasibility of biodiesel effluent treatment combining coagulation-flocculation with a photolytic process was evaluated, being the photolytic process involving the irradiation of the effluent by UV-C, or by UV-C irradiation with simultaneous addition of H2O2 (H2O2/UV-C). The coagulation-flocculation was performed at the natural pH of the effluent (pH 2.9) using different Fe3+ salts (chloride, nitrate and sulfate) at different concentrations (0.25, 0.50 and 1.0 mmol L-1) of the counterions. The best results were achieved using 0.50 mmol L-1 Fe(NO3)3. Following, the degradation of the organic load and toxicity reduction of the pre-treated effluent by UV-C irradiation was evaluated. The H2O2/UV-C process showed to be advantageous, mainly when multiple additions of H2O2 were used during the course of the reaction. Additionally, the influence of the initial pH on the degradation was also evaluated. A high level of mineralization (94%) was achieved after 6 h of irradiation concomitantly with multiple additions of 2,000 mg L-1 H2O2, and with the effluent at the natural pH. Thus, using coagulation-flocculation followed by the H2O2/UV-C process, it was possible to achieve a favourable condition for reuse of the pre-treated effluent, since, in addition to the significant reduction of the organic load, the final DBO5 (<120 mg L-1) and oils & fats (<50 mg L-1) are below the limits established by the Brazilian legislation. Furthermore, a reduction of 78% of acute toxicity to V. fischeri (from 89% to 20%) was reached. The results suggest, therefore, that this process is a viable option for treatment of this kind of effluent.

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The role of different operational parameters related to Fenton reactions (pH, concentration of Fe2+ and H2O2, and reaction time) and of Cl- and SO 4- was investigated in the degradation of the azo dye Direct Red 81, expressed in terms of its decolorization. The factorial design and Pareto's charts showed that only Fe2+ concentration and pH influence the decolorization under the conditions evaluated. So, only these parameters were optimized using the response surface model. Under the best experimental conditions (initial pH 2.5, 11 mg L-1 Fe2+, 78 mg L-1 H2O2, and 20 min of reaction), 94 % of decolorization was achieved. However, even under the these conditions, but in the presence of Cl- and SO 4- , a striking loss of efficiency was observed as the concentration of these ions was increased, due the formation of chloride- and sulfate-iron complexes and less reactive inorganic radicals (Cl2•- and SO4•-). The results show that the presence of Cl- is more deleterious, since sulfate-iron complexes are more reactive towards H2O2, and the SO4•- turns out to favor the degradation. On the other hand, the  negative effect of Cl- can be compensated by increasing the chloride concentration up to 300 mmol L-1. In addition, although a high degradation level has been obtained by monitoring the dye absorbance and by HPLC-UV, a low mineralization occurred, being generated degradation products of higher ecotoxicity to Vibrio fischeri, showing the need of subsequent studies to identify these compounds as well as the application of additional treatments aiming the complete mineralization of the dye.

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The degradation of caffeine in different kind of effluents, via photo-Fenton process, was investigated in lab-scale and in a solar pilot plant. The treatment conditions (caffeine, Fe(2+) and H(2)O(2) concentrations) were defined by experimental design. The optimized conditions for each variable, obtained using the response factor (% mineralization), were: 52.0 mg L(-1)caffeine, 10.0 mg L(-1)Fe(2+) and 42.0 mg L(-1)H(2)O(2) (replaced in kinetic experiments). Under these conditions, in ultrapure water (UW), the caffeine concentration reached the quantitation limit (0.76 mg L(-1)) after 20 min, and 78% of mineralization was obtained respectively after 120 min of reaction. Using the same conditions, the matrix influence (surface water - SW and sewage treatment plant effluent - STP) on caffeine degradation was also evaluated. The total removal of caffeine in SW was reached at the same time in UW (after 20 min), while 40 min were necessary in STP. Although lower mineralization rates were verified for high organic load, under the same operational conditions, less H(2)O(2) was necessary to mineralize the dissolved organic carbon as the initial organic load increases. A high efficiency of the photo-Fenton process was also observed in caffeine degradation by solar photocatalysis using a CPC reactor, as well as intermediates of low toxicity, demonstrating that photo-Fenton process can be a viable alternative for caffeine removal in wastewater.

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An imidazolium tetrasubstituted cationic porphyrin derivative (the free base and its Zn(II) complex) with five-membered heterocyclic groups in the meso-positions were synthesized using microwave irradiation, and the compounds obtained characterized by (1)H-NMR and mass spectrometry. We observed that under microwave irradiation the yield is similar to when the synthesis is performed under conventional heating, however, the time required to prepare the porphyrins decreases enormously. In order to investigate the electronic state of these compounds, we employed UV-Vis and fluorescence spectroscopy combined with quantum chemical calculations. The results reveal the presence, in both compounds, of a large number of electronic states involving the association between the Soret and a blue-shifted band. The Soret band in both compounds also shows a considerable solvent dependence. As for emission, these compounds present low quantum yield at room temperature and no solvent influence on the fluorescence spectra was observed.

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The in vitro photoinactivation of human tumor cell lines and sheep red blood cells (SRBC) by Zinc (II) Phthalocyanine (ZnPc) was investigated using unilamellar liposome (LUV) as delivery system, in the presence and absence of cholesterol (CHOL) in the formulation. The presence of CHOL improves the stability of the system showing to be essential for the photodynamic action of ZnPc. LUVs prepared without CHOL did not present any antiproliferative effects neither induced significant photohaemolysis. The presence of ZnPc in the culture medium caused total cell growth inhibition (TGI) only at concentrations higher than 250 micromol dm(-3). For ZnPc in LUV/CHOL (mass ratio=3:1), the mean TGI values for almost all studied cells were around 80 micromol dm(-3), and 14 micromol dm(-3) for human ovarian carcinoma (NIH: OVCAR-3) cells. The cytoplasmic components of OVCAR-3 and SRBC when irradiated in presence of ZnPc in LUV/CHOL were completely destroyed, culminating in cell swelling, lysis and death by necrosis.

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