Role of Nitrite Ions and Natural Organic Matters as Photosensitizers on Photolysis of Phenol

2014 ◽  
Vol 926-930 ◽  
pp. 226-229 ◽  
Author(s):  
Chen Liang ◽  
Hui Min Zhao ◽  
Min Jie Deng ◽  
Xie Quan ◽  
Shuo Chen
Keyword(s):  
Organic Pollutants ◽  
Natural Waters ◽  
Pure Water ◽  
Paramagnetic Resonance ◽  
Organic Matters ◽  
Model Molecule ◽  
Natural Organic Matters ◽  
Electron Paramagnetic ◽  
Photolysis Of Phenol

Nitrite and natural organic matters (NOM) are well known to be involved in photochemical processes occurring in natural waters. In this study, phenol is chosen as model molecule to investigate the role of nitrite ions or NOM towards the transformation of organic matters in aqueous solutions under simulated sunlight irradiation. All experiments were performed in pure water at pH 7. The results indicated that phenol phototransformation rate increased with increasing nitrite or NOM concentrations as expected. And •OH radical was demonstrated to be the main relative free radical according to the electron paramagnetic resonance (EPR) and isopropanol quenching experiments. But unexpectedly, the presence of NOM would inhibit nitrite ions-sensitized photolysis of phenol, and it might be attributed to the ROS quenching and light screening effect of NOM. The results imply that for accurate ecological risk assessment of organic pollutants, the integrated effect of water constituent on the environmental photochemical behavior of organic pollutants should not be ignored.

scholarly journals DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites

2018 ◽  
Vol 4 (4) ◽  
pp. 55 ◽  
Author(s):  
Giuseppe Sciortino ◽  
Giuseppe Lubinu ◽  
Jean-Didier Maréchal ◽  
Eugenio Garribba
Keyword(s):  
Binding Sites ◽  
Density Functional ◽  
Computational Procedure ◽  
Paramagnetic Resonance ◽  
Functional Theory ◽  
Protein Binding Sites ◽  
The Mean ◽  
Hamiltonian Parameters ◽  
Electron Paramagnetic

With the aim to provide a general protocol to interpret electron paramagnetic resonance (EPR) spectra of paramagnetic copper(II) coordination compounds, density functional theory (DFT) calculations of spin Hamiltonian parameters g and A for fourteen Cu(II) complexes with different charges, donor sets, and geometry were carried out using ORCA software. The performance of eleven functionals was tested, and on the basis of the mean absolute percent deviation (MAPD) and standard deviation (SD), the ranking of the functionals for Az is: B3LYP > B3PW91 ~ B3P86 > PBE0 > CAM-B3LYP > TPSSh > BH and HLYP > B2PLYP > MPW1PW91 > ω-B97x-D >> M06; and for gz is: PBE0 > BH and HLYP > B2PLYP > ω-B97x-D > B3PW91~B3LYP~B3P86 > CAM-B3LYP > TPSSh~MPW1PW91 >> M06. With B3LYP the MAPD with respect to A z exp t l is 8.6% with a SD of 4.2%, while with PBE0 the MAPD with respect to g z exp t l is 2.9% with a SD of 1.1%. The results of the validation confirm the fundamental role of the second order spin-orbit contribution to Az. The computational procedure was applied to predict the values of gz and Az of the adducts formed by Cu(II) with albumin and two fragments of prion protein, 106–126 and 180–193.

scholarly journals PQQ-Aza-Crown Ether Complexes as Biomimetics for Lanthanide and Calcium Dependent Alcohol Dehydrogenases

2021 ◽  
Author(s):  
Violeta A. Vetsova ◽  
Katherine R. Fisher ◽  
Henning Lumpe ◽  
Alexander Schäfer ◽  
Erik K. Schneider ◽  
...  
Keyword(s):  
Metal Ions ◽  
Gas Phase ◽  
Ion Mobility ◽  
Paramagnetic Resonance ◽  
Calcium Dependent ◽  
Lower Charge ◽  
Crown Ether Complexes ◽  
Recent Group ◽  
Electron Paramagnetic

<div>Understanding the role of metal ions in biology can lead to the development of new catalysts for</div><div>several industrially important transformations. Lanthanides are the most recent group of metal ions</div><div>that have been shown to be important in biology i.e. - in quinone-dependent methanol</div><div>dehydrogenases (MDH). Here we evaluate a pyrroloquinoline quinone and 1-aza-15-crown-5 based</div><div>ligand platform as scaffold for Ca2+ , Ba2+ , La3+ and Lu3+ biomimetics of MDH and we evaluate the</div><div>importance of ligand design, charge, size, counterions and base for the alcohol oxidation reaction</div><div>using NMR spectroscopy. In addition, we report a new straightforward synthetic route (3 steps</div><div>instead of 11 and 33% instead of 0.6% yield) for biomimetic ligands based on PQQ. We show that</div><div>when studying biomimetics for MDH, larger metal ions and those with lower charge in this case</div><div>promote the dehydrogenation reaction more effectively and that this is likely an effect of the ligand</div><div>design which must be considered when studying biomimetics. To gain more information on the</div><div>structures and impact of counterions of the complexes, we performed collision induced dissociation</div><div>(CID) experiments and observe that the nitrates are more tightly bound than the triflates. To resolve</div><div>the structure of the complexes in the gas phase we combined DFT-calculations and ion mobility</div><div>measurements (IMS). Furthermore, we characterized the obtained complexes and reaction mixtures</div><div>using Electron Paramagnetic Resonance (EPR) spectroscopy and show the emergence of a quinone-</div><div>based radical during the reaction with substrate and base.</div>

Sources and implications of basal nitric oxide in spontaneous contractions of guinea pig taenia caeci

2003 ◽  
Vol 285 (4) ◽  
pp. G747-G753 ◽  
Author(s):  
Catalina Caballero-Alomar ◽  
Carmen Santos ◽  
Diego Lopez ◽  
M. Teresa Mitjavila ◽  
Pere Puig-Parellada
Keyword(s):  
Nitric Oxide ◽  
Guinea Pig ◽  
Inhibitory Effect ◽  
No Production ◽  
Paramagnetic Resonance ◽  
Synthase Inhibitor ◽  
Spontaneous Contractions ◽  
Electron Paramagnetic

We examined in vitro the source and role of basal nitric oxide (NO) in proximal segments of guinea pig taenia caeci in nonadrenergic, noncholinergic (NANC) conditions. Using electron paramagnetic resonance (EPR), we measured the effect of the NO synthase inhibitor NG-nitro-l-arginine methyl ester (l-NAME, 10–4 M), the neuronal blocker tetrodotoxin (TTX, 10–6 M), or both on spontaneous contractions and on the production of basal NO. Both l-NAME and TTX, when tested alone, increased the amplitude and frequency of contractions. NO production was abolished by l-NAME and was inhibited by 38% by TTX. When tested together, l-NAME in the presence of TTX or TTX in the presence of l-NAME had no further effect on the amplitude or frequency of spontaneous contractions, and the NO production was inhibited. These findings suggest that basal NO consists of TTX-sensitive and TTX-resistant components. The TTX-sensitive NO has an inhibitory effect on spontaneous contractions; the role of TTX-resistant NO is unknown.

Improved (Photo)catalytic Propene Hydration in a Gas/Solid System by Using Heteropolyacid/Oxide Composites: Electron Paramagnetic Resonance, Acidity, and Role of Water

2017 ◽  
Vol 2017 (13) ◽  
pp. 1900-1907 ◽  
Author(s):  
Elisa I. García-López ◽  
Giuseppe Marcì ◽  
Francesca R. Pomilla ◽  
Leonarda F. Liotta ◽  
Bartolomeo Megna ◽  
...  
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Paramagnetic Resonance ◽  
Oxide Composites ◽  
Electron Paramagnetic ◽  
Solid System
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