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O trabalho está relacionado com a degradação fotocatalítica da acetamipride, uma base piridínica amplamente utilizada em inseticida neonicotinóides, em suspensões aquosas de O 2 /TiO 2 irradiada por UV. A taxa de degradação foi estudada por HPLC/DAD e espectrofotometria UV. Verificou-se que a reação é de pseudo-primeira ordem, no intervalo de concentração de (0,5-2,0 mg cm-3). A análise de RMN de 1 H indicou que além do acetaldeído, ácido fórmico e acético, foram formados intermediários contendo piridina (por exemplo, o ácido 6-chloronicotínico). Medidas por CLAE/EM revelaram também a presença da degradação de aromáticos intermediários. Durante o processo fotocatalítico o pH sofreu alteração de três unidades, de 5 a 2. Em contraste com os resultados obtidos nas condições experimentais na degradação fotocatalítica, a acetamipride mostrou-se estável. Para ter uma visão específica do complexo processo fotocatalítico da acetamipride, a degradação fotocatalítica do ácido 6-cloronicotínico, também foi investigada o produto detectado da degradação da base piridínica. The work is concerned with the photocatalytic degradation of acetamiprid, a widely used pyridine-based neonicotinoid insecticide, in UV-irradiated aqueous suspensions of O 2 /TiO 2. The rate of degradation was studied by HPLC/DAD and UV spectrophotometry. It was found that the reaction in the investigated concentration range (0.5-2.0 mg cm-3) is of a pseudo-first order. The 1 H NMR analysis indicated that beside acetaldehyde, formic and acetic acid, pyridine-containing intermediates (e.g. 6-chloronicotinic acid) formed during the process. The HPLC/MS measurements also proved the presence of aromatic degradation intermediates. During the photocatalytic process the pH changed by even three units, from 5 to 2. In contrast to the photocatalytic results in the photolytic experimental conditions, acetamiprid appeared to be stable. To get a deeper insight into the complex photocatalytic process of acetamiprid, the photocatalytic degradation of 6-chloronicotinic acid, the detected pyridine-based degradation product, was also investigated.

Voltammetric behavior of erythromycin ethylsuccinate at a renewable silver-amalgam film electrode and its determination in urine and in a pharmaceutical preparation, Electrochimica Acta http://dx.2 Graphical abstract 3 Highlights  Voltammetric characterization of erythromycin ethylsuccinate (EES) on Hg(Ag)FE  Trace level determination of EES by electroreduction based SWV and SW-AdSV methods  Protonation of the tertiary amino group supports the adsorption of EES on Hg(Ag)FE  1 H NMR confirms chemical shifting of tertiary amine methyl proton signals with pH  Comparative HPLC-DAD measurements were performed for the validation of the methods 4 AbstractErythromycin, a macrolide antibiotic, has similar antimicrobial spectrum to penicillin and it is widely used, especially in the treatment of patients who are allergic to penicillin.In this work, the application of a renewable silver-amalgam film electrode (Hg (Ag)FE) for the characterization and determination of erythromycin ethylsuccinate (EES), a widely used esterified form of this antibiotic, by means of cyclic voltammetry (CV) and square wave voltammetry (SWV) is presented. In the aqueous Britton-Robinson buffer (pH 5.0-9.0) that served as the supporting electrolyte, one reduction peak of EES was observed in the investigated potential range between -0.75 V and -1.80 V vs SCE, with peak potential maxima ranging from -1.59 V to -1.70 V, which strongly depended on the applied pH, as did the peak shape. For the analytical purposes the pH of 7.0 was selected, since in this electrolyte the EES peak was well-shaped and separated from the background current of the supporting electrolyte in both cases; in the direct cathodic SWV and in the case of square wave adsorptive stripping voltammetry (SW-AdSV). It was established, by the Ep-pH correlation, that protons strongly influenced the electrochemical reduction of EES. The CVs recorded between 0.025 -0.50 V s -1 at pH 7.0 confirmed that the electrode reaction is adsorption-controlled. Based on the series of 1 H NMR measurements it is proved that the tertiary amino group of EES is mainly in its protonated form at pH 7.0 which may lead, at appropriate accumulation potential and time, to the favored adsorption of the target ionic form of the analyte improving on such way the sensitivity of the SW-AdSV method.The optimized procedures resulted in stable SWV responses with good linear correlation in the EES concentration range from 4.53 to 29.8 µg mL -1 (LOD = 1.36 µg mL -1 ), and from 0.69 µg mL -1 to 2.44 µg mL -1 (LOD 0.21 µg mL -1 ) in the case of optimized SWAdSV. The relative standard deviation is below 1.5%. The reliability of the elaborated procedures and thus the accuracy of the obtained results were validated by comparing them with those obtained by means of HPLC-DAD measurements. The direct cathodic SWV method was successfully applied for the determination of EES in the pharmaceutical preparation Eritromicin ® , while SW-AdSV was applied in the case of the spiked urine sample.In both cases, the standard addition meth...

In this work a 1-(2-hydroxyethyl)-3-methylimidazolium nitrate ionic liquid, [HO(CH2)2mim]NO3, has been synthesized in order to serve as a new thermochromic material upon addition of cobalt(II) ions. Spectrophotometric measurements of a series of cobalt(II) nitrate and cobalt(II) chloride solutions in [HO(CH2)2mim]NO3 at 298.15, 308.15, 318.15, 328.15, and 338.15 K, were performed. Based on the recorded spectra, the overall stability constants and thermodynamic parameters for the cobalt(II) associations with chloride and nitrate ions were calculated. The thermodynamic calculations suggest that thermochromism is not observed in the ionic medium due to a small entropy change during the replacement of nitrate with chloride ions in the co-ordination sphere of cobalt(II). The absence of the molecular solvent was also the reason for the lack of thermochromism. Thus, cobalt(II) solutions in [HO(CH2)2mim]NO3 and water mixtures were studied as a new and green medium that can be used for the auto-regulation of the light intensity and shade protection. The investigated system with water upon addition of cobalt(II) was found to be a far more efficient and responsive thermochromic medium for all of the studied systems up until now. The structure of [HO(CH2)2mim]NO3 was confirmed by both (1)H NMR and IR spectroscopy. Also, the efficiency of different advanced oxidation processes (UV-induced photolysis, UV/H2O2 photolysis, heterogeneous photocatalysis using TiO2 Degussa P25 and TiO2 with 7.24%, w/w Fe catalysts) for [HO(CH2)2mim]NO3 degradation were investigated. The reaction intermediates formed during the photo-oxidation process were identified using LC-ESI-MS/MS and (1)H NMR techniques.