Photodegradation, toxicity and density functional theory study of pharmaceutical metoclopramide and its photoproducts.

Pharmaceuticals as ubiquitous organic pollutants in the aquatic environment represent substances whose knowledge of environmental fate is still limited. One such compound is metoclopramide, whose direct and indirect photolysis and toxicological assessment have been studied for the first time in this study. Experiments were performed under solar radiation, showing metoclopramide as a compound that can easily degrade in different water matrices. The effect of pH-values showed the faster degradation at pH = 7, while the highly alkaline conditions at pH = 11 slowed photolysis. The highest value of quantum yield of metoclopramide photodegradation (ϕ = 43.55·10-4) was obtained at pH = 7. Various organic and inorganic substances (NO3-, Fe(III), HA, Cl-, Br-, HCO3-, SO42-), commonly present in natural water, inhibited the degradation by absorbing light. In all experiments, kinetics followed pseudo-first-order reaction with r2 greater than 0.98. The structures of the photolytic degradation products were tentatively identified, and degradation photoproducts were proposed. The hydroxylation of the aromatic ring and the amino group's dealkylation were two major photoproduct formation mechanisms. Calculated thermochemical quantities are in agreement with the experimentally observed stability of different photoproducts. Reactive sites in metoclopramide were studied with conceptual density functional theory and regions most susceptible to •OH attack were characterized. Metoclopramide and its degradation products were neither genotoxic for bacteria Salmonella typhimurium in the SOS/umuC assay nor acutely toxic for bacteria Vibrio fischeri.

Effects of environmental factors on nitrofurantoin photolysis in water and its acute toxicity assessment.

Pharmaceuticals have special attention of researchers over the world due to their possible effect on the environment and humans. This paper focuses on the photolysis of nitrofurantoin in different water matrices. Nitrofurantoin photodegradation has been indicated as a pseudo-first order photoreaction. The indirect photodegradation rate of nitrofurantoin (river water, k1 = 0.0088 min-1 and synthetic wastewater, k1 = 0.0154 min-1) was slower than its direct photolysis rate (ultrapure water, k1 = 0.0176 min-1). The highest value of quantum yield of nitrofurantoin photodegradation (ϕ = 0.2047) was observed at pH = 4, while at higher pH-values it decreased. Furthermore, the mechanism of nitrofurantoin photodegradation is proposed. Heterocyclic ring opening and further hydrolysis, nucleophilic aromatic photosubstitution and homolytic N-N bond cleavage are suggested as three main initial processes of nitrofurantoin photodegradation. Acute toxicity study of nitrofurantoin and its photoproducts with regard to luminescence inhibition of Vibrio fischeri showed that the toxic effect of nitrofurantoin (EC50 = 4.0 mg L-1) decreases by photolysis.

Tailoring the stability/aggregation of one-dimensional TiO2(B)/titanate nanowires using surfactants.

The increased utilization of one-dimensional (1D) TiO2 and titanate nanowires (TNWs) in various applications was the motivation behind studying their stability in this work, given that stability greatly influences both the success of the application and the environmental impact. Due to their high abundance in aqueous environments and their rich technological applicability, surfactants are among the most interesting compounds used for tailoring the stability. The aim of this paper is to determine the influence of surfactant molecular structure on TNW stability/aggregation behavior in water and aqueous NaBr solution by dynamic and electrophoretic light scattering. To accomplish this, two structurally different quaternary ammonium surfactants (monomeric DTAB and the corresponding dimeric 12-2-12) at monomer and micellar concentrations were used to investigate TNW stability in water and NaBr. It was shown that TNWs are relatively stable in Milli-Q water. However, the addition of NaBr induces aggregation, especially as the TNW mass concentration increases. DTAB and 12-2-12 adsorb on TNW surfaces as a result of the superposition of favorable electrostatic and hydrophobic interactions. As expected, the interaction of TNWs with 12-2-12 was stronger than with DTAB, due to the presence of two positively charged head groups and two hydrophobic tails. As a consequence of the higher adsorption of 12-2-12, TNWs remained stable in both media, while DTAB showed an opposite behavior. In order to gain more insight into changes in the surface properties after surfactant adsorption on the TNW surface, a surface complexation model was employed. With this first attempt to quantify the contribution of the surfactant structure on the adsorption equilibrium according to the observed differences in the intrinsic log K values, it was shown that 12-2-12 interacts more strongly with TNWs than DTAB. The modelling results enable a better understanding of the interaction between TNWs and surfactants as well as the prediction of the conditions that can promote stabilization or aggregation.

The role of photodegradation in the environmental fate of hydroxychloroquine.

For many organic pollutants present in surface waters, photolysis is considered as a major abiotic degradation process. The present study aimed to explore the role of photolysis in the environmental fate of hydroxychloroquine (HCQ) for the first time. The photolytic degradation of HCQ was investigated under simulated solar radiation (300-800 nm) in ultrapure, spring, river, and sea water. The effect of pH on the photodegradation rate was substantial and it was observed that degradation was faster at higher pH-values. Obtained half-lives ranged from 5.5 min at pH 9 to 23.1 h at pH 4. Humic acids, nitrate and iron(III) enhanced photodegradation of HCQ due to formation of hydroxyl radicals and its attack on HCQ molecule. In contrast, chloride, sulfate and bromide inhibited photodegradation. Additionally, the humic acids exhibited a dual role, photosensitization and inner filter effect. The study of the reaction kinetics was performed with HPLC-PDA, while the identification of degradation products formed during photolytic degradation was carried out using HPLC-MS/MS and NMR spectroscopy. The hydroxylation was recognized as the dominant path of photoproducts formation. The results of this research reveal the importance of photolytic degradation in environmental fate of HCQ and enable a better understanding of its behavior in the environment. Moreover, the results showing the significant effect of pH on the photodegradation of HCQ can be very useful in water treatment processes.

The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations.

Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc)2, depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na+ cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na+ cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. Graphical Abstract ᅟ.