A study of the photocatalytic degradation of methomyl by UV light

The photocatalytic degradation of insecticide methomyl in water, using TiO2 and ZnO (Merck), under UV (366 nm) was studied. The influence of the catalyst concentration and pH was investigated. The optimal concentration of the catalyst was found to be 2.0 g/l. It was found that ZnO is a better catalyst than TiO2 under the same reaction conditions. Also, the influence of NaCl was studied. The presence of Cl− significantly affects the photodegradation of the pollutant

Enzymatic synthesis of vitamin B6 precursor

3-Cyano-4-ethoxymethyl-6-methyl-2-pyridone is an important precursor in the synthesis of vitamin B6, obtained in the addition reaction between 2-cyanoacetamide and 1-ethoxy-2,4-pentanedione catalyzed by lipase from Candida rugosa (triacylglycerol ester hydrolases, EC 3.1.1.3). This work shows new experimental data and mathematical modeling of lipase catalyzed synthesis of 3-cyano-4-ethoxymethyl-6-methyl-2-pyridone, starting from 1-ethoxy-2,4-pentanedione and 2-cyanoacetamide. Kinetic measurements were done at 50 oC with enzyme concentration of 1.2 % w/v. Experimental results were fitted with two kinetic models: the ordered bi-ter and ping-pong bi-ter model, and the initial rates of the reaction were found to correlate best with a ping-pong bi-ter mechanism with inhibition by 2-cyanoacetamide. Obtained specificity constants indicated that lipase from C. rugosa had higher affinity towards 1-ethoxy-2,4-pentanedione and less bulky substrates. [Projekat Ministarstva nauke Republike Srbije, br. 172013, br. III 46010 and br. 172049

Voltammetric and Square-Wave Anodic Stripping Determination of Amlodipine Besylate on Gold Electrode

The oxidative behaviour of amlodipine besylate was studied. The gold electrode and Au/o-MWCNT (oxidized multi-wall carbon nanotubes) were used for determination of amlodipine besylate standard and as a content of Alopres tablet, in 0.05 M NaHCO3 and in phosphate buffer (pH=11) by cyclic voltammetry and square-wave anodic stripping voltammetry. Electrode surfaces were characterized by AFM in the presence of amlodipine and the concentrations of drugs in electrolytes were simultaneously followed by HPLC. The linear dependency of the anodic currents of amlodipine besylate as standard and in Alopres tablet vs. concentration was observed in both electrolytes, but in phosphate buffer for the higher concentrations. The peak currents obtained in all experiments are more than fifty-fold higher comparing to all previously published results concerning the glassy carbon electrode and the carbon paste electrode. The gold electrode is better catalyst for anodic oxidation of amlodipine besylate than glassy carbone. The results obtained with Au/o-MWCNT show lower anodic activity comparing to previously published GC/o-MWCNT. GC/o-MWCNT is better catalyst than Au/o-MWCNT under similar experimental conditions

Uticaj supstituenata na IR, 1H- i 13C-NMR spektralne podatke N-(supstituisanih fenil)-2-cijanoacetamida - korelaciona analiza

Linear free energy relationships (LFER) were applied to the IR, H-1- and C-13-NMR spectral data of N-(substituted phenyl)-2-cyanoacetamides. A variety of substituents were employed for phenyl substitution and fairly good correlations were obtained using the simple Hammett and the Hammett-Taft dual substituent parameter equations. The correlation results of the substituent induced C-13-NMR chemical shifts (SCS) of the Cl, C=O and N-H atom indicated different sensitivity with respect to electronic substituent effects. A better correlation of the SCSc=O with a combination of electrophllic and nucleophilic substituent constants indicated a significant contribution of extended resonance interaction (pi-delocalization) within the pi(1)-unit. The conformations of the investigated compounds were studied using the OFT B3LYP/6-311G** method and, together with the results of C-13-NMR and IR spectroscopic studies, a better insight into the influence of such a structure on the transmission of electronic substituent effects was obtained.Principi linearnih korelacija slobodnih energija (LFER) su primenjeni na IR, 1H- i 13C-NMR spektralne podatke N-(supstituisanih fenil)-2-cijanoacetamida. Pri sintezi N-(supstituisanih fenil)-2-cijanoacetamida izvršen je zadovoljavajući izbor supstituenata u pogledu elektronskih svojstava kako bi se adekvatno sagledao uticaj elektronskih efekata supstituenata na pomeranja u IR, 1H- i 13C-NMR spektralnim podacima. Primenom proste Hametove jednačine dobijene su zadovoljavajuće korelacije. Na osnovu korelacionih rezultata uočen je primaran uticaj elektronskih efekata na SCS (supstituentom indukovana hemijska pomeranja) vrednosti N-H vodonika, C1 i C=O ugljenika ispitivanih jedinjenja. Korelacioni rezultati za C=O ugljenik se značajno popravljaju ako se koristi kombinacija Ϭ+ i Ϭ- konstanti supstituenata, takozvane elektrofilne i nukleofilne konstante supstituenata, što ukazuje na postojanje značajne proširene rezonancione interakcije supstituenata i elektronske gustine karbonilne grupe. Vrednosti konstanti proporcionalnosti pF i pR za sve atome, ukazuju na približno isti doprinos efekta polja i rezonancionog efekta supstituenata. Efekat polja je nešto izraženji na N-H vodoniku, i za sve atome pokazuje značajne razlike u odnosu na njihov položaj u molekulskoj strukturi ispitivanih jedinjenja. Uticaj efekata supstituenata na IR vibracije istezanja N-H (simetrične i antisimetrične), C=O i CN veze je prevashodno elektronske prirode što se može zaključiti na osnovu dobrih korelacija dobijenih primenom Hametove jednačine i Ϭ parametara supstituenata. Osim toga izvršena je optimizacija geometrije ispitivanih jedinjenja primenom DFT B3LYP/ 6-311G**metode, pri čemu je nađeno da je trans-izomer nešto stabilnji, izuzev u slučaju jedinjenja 3. Supstituisana fenil-grupa i amidna grupa, kod trans-izomera, su približno koplanarne, dok se kod cis- izomera uočava značajna devijacija koja je značajno određena elektronskim efektima prisutnog supstituenta. Takođe je ispitivan položaj cis/trans ravnoteže u ugjen-tetrahloridu, i na osnovu rezultata FT/R analize, kada je prisutan H, CH3, OCH3, Br, i COOH supstituent, nađeno je da je cis izomer u velikom višku, a za ostala jedinjenja utvrđeno je postojanje ravnoteže cis- i trans-izomera

The electrochemical investigation of inclusion complexes of nifedipine and amlodipine with ß-cyclodextrin and (2-hydroxypropyl)-ß-cyclodextrin

The electrochemical behavior of inclusion complexes of nifedipine (Nif) and amlodipine (Aml), a long-acting calcium channel blockers dihydropyridine (DHP) class, with ß-cyclodextrin (ßCD) and (2-hydroxypropyl)-ß-cyclodextrin (HPßCD), is examined using cyclic and square wave voltammetry in 0.05 M NaHCO3 and phosphate buffer (pH=11) on a gold electrode. The voltammograms show a single irreversible anodic wave with the current controlled by adsorption. It was found that phosphate buffer favorites the electrochemical activity of both complexes of Nif with the linear dependency of the oxidative currents on their concentrations. In phosphate buffer, only HPßCD-Aml complex showed linear dependency of the oxidative currents on the concentration. In 0.05 M NaHCO3 as electrolyte only HPßCD-Nif exhibited apparent activity. The initial potential of the anodic reaction as well as the value of the potential for anodic currents maximum of all the examined complexes in both electrolytes were shifted to the positive direction compared to their standards. In addition, the value of anodic currents decreased

Photodegradation of dimethenamid-p in deionised and ground water

The study of photodegradation of dimethenamid-P herbicide was performed in deionised and ground water using TiO2 as a catalyst under UV light. The effect of electron acceptor (H2O2), scavenger of (OH)-O-center dot radicals (C2H5OH) and scavenger of holes (NaCl and Na2SO4) as well as solution pH was analyzed. The photodegradation of dimethenamid-P was followed by HPLC. The formation of transformation products was followed using high performance liquid chromatography-electrospray mass spectrometry. Ion chromatography and total organic carbon measurements were used for the determination of the mineralization level. HPLC analysis showed the almost complete removal of herbicide after 90 min in deionised and ground water, while total organic carbon analysis showed that dimethenamid-P was mineralized 64 and 50% in deionised and ground water, respectively. The ion chromatography results showed that the mineralization process leads to the formation of chloride, sulphate and nitrate anions during the process. Transformation products were identified and the degradation mechanism was proposed

Multi-machine benchmark of the self-consistent 1D scrape-off layer model DIV1D from stagnation point to target with SOLPS-ITER

This paper extends a 1D dynamic physics-based model of the scrape-off layer (SOL) plasma, DIV1D, to include the core SOL and possibly a second target. The extended model is benchmarked on 1D mapped SOLPS-ITER simulations to find input settings for DIV1D that allow it to describe SOL plasmas from upstream to target—calibrating it on a scenario and device basis. The benchmark shows a quantitative match between DIV1D and 1D mapped SOLPS-ITER profiles for the heat flux, electron temperature, and electron density within roughly 50% on: (1) the Tokamak Configuration Variable (TCV) for a gas puff scan; (2) a single SOLPS-ITER simulation of the Upgraded Mega Ampere Spherical Tokamak; and (3) the Upgraded Axially Symmetric Divertor EXperiment in Garching Tokamak (AUG) for a simultaneous scan in heating power and gas puff. Once calibrated, DIV1D self-consistently describes dependencies of the SOL solution on core fluxes and external neutral gas densities for a density scan on TCV whereas a varying SOL width is used in DIV1D for AUG to match a simultaneous change in power and density. The ability to calibrate DIV1D on a scenario and device basis is enabled by accounting for cross field transport with an effective flux expansion factor and by allowing neutrals to be exchanged between SOL and adjacent domains.</p