Oxidation In Media Research Articles

Selective shortening of gold nanorods: when surface functionalization dictates the reactivity of nanostructures.

The selective shortening of gold nanorods (NRs) is a directional etching process that has been intensively studied by UV-Vis spectroscopy because of its direct impact on the optical response of these plasmonic nanostructures. Here, liquid-cell transmission electron microscopy is exploited to visualize this peculiar corrosion process at the nanoscale and study the impacts of reaction kinetics on the etching mechanisms. In situ imaging reveals that anisotropic etching requires a chemical environment with a low etching power to make the tips of NRs the only reaction site for the oxidation process. Then, aberration-corrected TEM and atomistic simulations were combined to demonstrate that the disparity between the reactivity of the body and the ends of NRs does not derive from their crystal structure but results from an inhomogeneous surface functionalization. In a general manner, this work highlights the necessity to consider the organic/inorganic natures of nanostructures to understand their chemical reactivity.

Determination of Chemical Stability of Two Oral Antidiabetics, Metformin and Repaglinide in the Solid State and Solutions Using LC-UV, LC-MS, and FT-IR Methods.

Firstly, metformin and repaglinide were degraded under high temperature/humidity, UV/VIS light, in different pH and oxidative conditions. Secondly, a new validated LC-UV method was examined, as to whether it validly determined these drugs in the presence of their degradation products and whether it is suitable for estimating degradation kinetics. Finally, the respective LC-MS method was used to identify the degradation products. In addition, using FT-IR method, the stability of metformin and repaglinide was scrutinized in the presence of polyvinylpyrrolidone (PVP), mannitol, magnesium stearate, and lactose. Significant degradation of metformin, following the first order kinetics, was observed in alkaline medium. In the case of repaglinide, the most significant and quickest degradation, following the first order kinetics, was observed in acidic and oxidative media (0.1 M HCl and 3% H2O2). Two new degradation products of metformin and nine new degradation products of repaglinide were detected and identified when the stressed samples were examined by our LC-MS method. What is more, the presence of PVP, mannitol, and magnesium stearate proved to affect the stability of metformin, while repaglinide stability was affected in the presence of PVP and magnesium stearate.

Titanium - castor oil based polyurethane composite foams for bone tissue engineering

Polyurethanes (PU) foams with titanium particles (Ti) were prepared with castor oil (CO) and isophorone diisocyanate (IPDI) as polymeric matrix, and 1, 3 and 5 wt.% of Ti. Composites were physicochemically and mechanically characterized and their biocompatibility assessed using human dental pulp stem cells (HDPSC). PU synthesis was confirmed by FTIR, but the presence of Ti was detected by RAMAN, X-ray diffraction (peak at 2θ = 40.2°) and by EDX-mapping. Materials showed three decomposition temperatures between 300 °C and 500 °C and their decomposition were not catalyzed by Ti particles. Compressive modulus (164–846 kPa), compressive strength (12.9–116.7 kPa) and density (128–240 kg/m3) tend to increase with Ti concentration but porosity was reduced (87% to 80%). Composites’ foams were fully degraded in acid and oxidative media while remained stable in distilled water. HDPSC viability on all composites was higher than 80% up to 14 days while proliferation dropped up to 60% at 21 days. Overall, these results suggest that these foams can be used as scaffolds for bone tissue regeneration.

Stimulus-Responsive Anti-Oxidizing Drug Crystals and their Ecological Implication.

Various antioxidants are being used to neutralize the harmful effects of reactive oxygen species (ROS) overproduced in diseased tissues and contaminated environments. Polymer-directed crystallization of antioxidants has attracted attention as a way to control drug efficacy through molecular dissolution. However, most recrystallized antioxidants undertake continuous dissolution independent of the ROS level, thus causing side-effects. This study demonstrates a unique method to assemble antioxidant crystals that modulate their dissolution rate in response to the ROS level. We hypothesized that antioxidants recrystallized using a ROS-labile polymer would be triggered to dissolve when the ROS level increases. We examined this hypothesis by using catechin as a model antioxidant. Catechin was recrystallized using polyethylenimine cross-linked with ROS-labile diselanediylbis-(ethane-2,1-diyl)-diacrylate. Catechin crystallized with the ROS-labile polymer displays accelerated dissolution proportional to the H2 O2 concentration. The ROS-responsive catechin crystals protect vascular cells from oxidative insults by activating intracellular glutathione peroxidase expression and, in turn, inhibiting an increase in the intracellular oxidative stress. In addition, ROS-responsive catechin crystals alleviate changes in the heart rate of Daphnia magna in oxidative media. We propose that the results of this study would be broadly useful for improving the therapeutic efficacy of a broad array of drug compounds.

Determination of chemical stability of sitagliptin by LC-UV, LC-MS and FT-IR methods

Sitagliptin was stored at high temperature/high humidity, dry hot air, UV/VIS light and different pH. Then, a selective LC-UV method was developed for determination of sitagliptin in the presence of degradation products and for estimation of degradation kinetics. Because parent drugs can react with excipients in final pharmaceutical formulations, stability of sitagliptin was also examined in the presence of excipients of different reactivity, using FT-IR and LC-UV methods. Finally, LC–MS method was used for identification of degradation products of sitagliptin.High degradation of sitagliptin, following the first order kinetics, was observed in strongly acidic, alkaline and oxidative media. The quickest degradation was found in 2 M HCl and 2 M NaOH. In addition, all excipients used in the present study, i.e. fumaric acid, lactose, mannitol and magnesium stearate showed potent interactions with sitagliptin. Some of these interactions were shown without any stress while others were accelerated by high temperature/high humidity and dry hot air, and less by UV/VIS light. Some mechanisms for the observed changes were proposed, i.e. the Michael addition in the presence of fumaric acid and the Maillard reaction in the presence of lactose. In addition, degradation of sitagliptin together with the occurrence of its impurities was stated in a broad range of stress conditions.

Effect of the rigid segment content on the properties of segmented polyurethanes conjugated with atorvastatin as chain extender.

Segmented polyurethanes were prepared with polycaprolactone diol as soft segment and various amounts of 4,4´-Methylenebis(cyclohexyl isocyanate) and atorvastatin, a statin used for lowering cholesterol, in order to obtain SPU with different content of rigid segments. Polyurethanes with 35% or 50% of rigid segment content were physicochemically characterized and their biocompatibility assessed with L929 fibroblasts. High concentrations of atorvastatin were incorporated by increasing the content of rigid segments as shown by FTIR, Raman, NMR, XPS and EDX. Thermal and mechanical characterization showed that polyurethanes containing atorvastatin and 35% of rigid segments were low modulus (13 MPa) semicrystalline polymers as they exhibited a glass transition temperature (Tg) at -38 °C, melting temperature (Tm) at 46 °C and crystallinity close to 35.9% as determined by DSC. In agreement with this, X-ray diffraction showed reflections at 21.3° and 23.6° for PCL without reflections for atorvastatin suggesting its presence in amorphous form with higher potential bioavailability. Low content of rigid segments led to highly degradable polymer in acidic, alkaline and oxidative media with an acceptable fibroblast cytotoxicity up to 7 days possibly due to low atorvastatin content.

Molecular Mn-catalysts grafted on graphitic carbon nitride (gCN): The behavior of gCN as support matrix in oxidation reactions

We report a synthetic methodology for covalent grafting of metal complexes with Schiff base ligands, on gCN as support. Based on this, the La@gCN-MnII and Lt@gCN-MnII materials have been prepared. Their physicochemical characterization suggested the successful immobilization of the entire [MnII-Schiff base] complexes on gCN without significant disturbance of ordered structure of the pristine gCN. The La@gCN-MnII and Lt@gCN-MnII were evaluated as catalysts for olefins’ epoxidations with H2O2. We found that they are efficient, selective towards epoxide formation and interestingly, the Lt@gCN-MnII was kinetically faster than the La@gCN-MnII. That is, the grafting process and the support environment offered by gCN maintain the catalytic performance of grafted molecular catalysts. Moreover, a detailed recycling study of the present catalytic materials has been done to investigate their robustness focusing on the textural features of the recovered and recycled catalysts. Our data showed an important matrix exfoliation occurs during oxidation catalysis indicating a limited stability of gCN as support material in oxidative media.

Study of degradation behaviour of montelukast sodium and its marketed formulation in oxidative and accelerated test conditions and prediction of physicochemical and ADMET properties of its degradation products using ADMET Predictor™

Study of oxidative stability of pharmaceutical actives and formulations is important as oxidation pathway is the second most significant route for the decay of pharmaceuticals. Montelukast sodium, a leukotriene receptor antagonist, is prone to oxidation reactions owing to sensitive moieties in its structure. It is also known to be light sensitive. This study was aimed to understand the degradation behaviour of the drug in different oxidative media containing hydrogen peroxide, AIBN, Fe3+, Fenton’s reagent and O2 environment under normal laboratory light conditions. The degradation behaviour of the drug was also evaluated in solid sate under ICH recommended accelerated stability condition of 40 °C/75% RH to correlate with the degradation products (DPs) formed in a solid oral formulation. A total of nine DPs (MTK 1 to MTK 9) were formed from both the drug substance and the marketed tablet formulation on storage under controlled oxygen environment in normal laboratory light and temperature conditions. These DPs were well separated on a C-18 column using a gradient HPLC method. The characterization of DPs was done based on HRMS and multi-stage tandem mass spectrometric (MSn) data. The knowledge of the structure of DPs helped in laying down degradation pathway of the drug. Also, mechanism for the formation of each DP was postulated. Finally, physicochemical as well as absorption, distribution, metabolism, excretion and toxicity (ADMET) properties of the DPs were predicted by ADMET Predictor™ software.

New approach for determination of the degradation products of fenspiride hydrochloride found in oral liquid formulations.

Fenspiride hydrochloride (FNS) is used in treating chronic inflammatory diseases, most commonly as a liquid oral solution. FNS produces degradation products along with fenspiride N-oxide (FNO) and 1-phenylethyl-4-hydroxy-4-aminomethyl piperidine hydrochloride (PHAP). We aimed to develop and validate a chromatographic method in order to identify the main degradation products in the presence of other compounds from a liquid preparation. The method used a dual gradient using two buffer solutions: the first with pH 4.5 (buffer 1, pH 4.5-MeOH 90:10%, v/v) and the second with pH 2.9 (buffer 2, pH 2.9-acetronitrile-methanol, 65:15:10%, v/v/v). As mentioned, there was a modification of the organic mixture, starting with 10% methanol and ending with a mixture of acetonitrile-methanol (15:10%, v/v). The flow-rate was 1.5 mL/min. According to the elution program, experimental conditions started with 100% solution S1, which decreased to 0% and, simultaneously, solution S2 increased to 100% during the first 10 min and was maintained for a further 5 min. After 15 min, initial conditions were re-established. The linearity interval was 0.5-2 μg/mL and the minimum correlation coefficient was 0.999. The recovery factor was 100.47-103.17% and the limit of quantification was 0.19-0.332 μg/mL. Intra-day maximum precision was 4.08% for FNS and 2.65% for PHAP. This double-gradient mobile phase produced good specificity in relation to the degradation products of FNS and other constituents of the oral liquid formulation. Forced degradation studies revealed other related substances that were confirmed in mass balance analyses. Degradation products were confirmed in acidic, basic and oxidative media.

Fate and hazard of the electrochemical oxidation of triclosan. Evaluation of polychlorodibenzo‑p‑dioxins and polychlorodibenzofurans (PCDD/Fs) formation

Triclosan (TCS) is widely used as antiseptic or preservative in many personal care products (PCPs), such as cosmetics, hand wash, toothpaste and deodorant soaps, among others. It is characterized by acute toxicity, resistance to biodegradation, environmental persistence and relatively high lipophilicity. In order to protect the environment and natural resources from the negative effects of the discharge of polluted wastewater with TCS, the application of efficient remediation technologies able to degrade the pollutant to harmless levels becomes crucial. Electrochemical oxidation, among all advanced oxidation processes (AOPs), has been reported as very effective in the complete degradation of a number of persistent pollutants; therefore, its performance using boron-doped diamond (BDD) anodes, and response to operation variables, has been studied in this work. As expected, complete degradation of TCS was achieved in all the studied conditions; however, going a step further and knowing that TCS is a precursor of polychlorinated dibenzo‑p‑dioxins and dibenzofurans (PCDD/Fs), their quantitative presence in the oxidation media has been assessed. Results showed the dominance of dichlorinated (DCDD) and trichlorinated (TrCDD/Fs) in the homologue profile of total PCDD/Fs, reaching values up to 1.48 × 105 pg L−1 in samples with initial concentration of TCS of 100 mg L−1 and NaCl as electrolyte. Under these conditions, the International Toxicity Equivalency Factor (I-TEF) achieved values up to 2.76 × 102 pg L−1. Nevertheless, the presence of copper in the oxidation medium tends to reduce I-TEF values. Finally, considering the information reported in literature, a mechanism describing the formation of low chlorinated PCDD/Fs from TCS oxidation reactions is proposed.

Thermodynamics of aqueous perfluorooctanoic acid (PFOA) and 4,8-dioxa-3H-perfluorononanoic acid (DONA) from DFT calculations: Insights into degradation initiation

Modern fluorosurfactants introduced during and after perfluoroalkyl carboxylates/sulfonates phase-out present chemical features designed to facilitate abatement, hence reducing persistence. However, the implications of such features on environmental partitioning and stability are yet to be fully appreciated, partly due to experimental difficulties inherent to the handling of their (diluted) aqueous solutions. In this work, rigorous quantum chemistry calculations were carried out in order to provide theoretical insights into the thermodynamics of hydroperfluorosurfactants in aqueous medium. Estimates of acid dissociation constant (pKa), standard reduction potential (E0), and bond dissociation enthalpy (BDE) and free energy (BDFE) were computed for perfluorooctanoic acid (PFOA), 4,8-dioxa-3H-perfluorononanoic acid (DONA) and their anionic forms via ensemble averaging at density functional theory level with implicit solvent models. A ‹pKa› in the neighborhood of zero and a E0 of about 2.2 V were obtained for PFOA. Predictions for the acidic function of DONA compare well with PFOA's, with a pKa of 0.8–1.5 and a E0 of 2.07–2.15 V. Deprotonation thus represents the dominant phenomenon at environmental conditions. Calculations indicate that H-abstraction of the aliphatic proton of DONA by a hydroxyl radical is the thermodynamically favored reaction path in oxidative media, whereas hydrolysis is not a realistic scenario due to the high dissociation constant. Short intramolecular interactions available to the peculiar hydrophobic tail of DONA were also reviewed, and the relevance of the full conformational space of the fluorinated side chain discussed.

Stripping Voltammetric Determination of Mercury in Fish Oil Capsules Using a Screen‐printed Gold Electrode

AbstractThis work presents a simple electrochemical method for Hg determination in fish oil capsules using anodic stripping voltammetry (ASV) on a screen‐printed gold electrode (SPGE). Samples were treated in an ultrasonic bath for 15 min in the presence of a 1 : 1 (v/v) concentrated HCl/H2O2 mixture at room temperature. The limit of detection (LOD) was estimated as 0.25 μg L−1 (corresponding to 7.6 μg kg−1 of oil) with a linear range between 5 and 400 μg L−1 (90 s of deposition time). The analyzed fish oil samples presented Hg concentration below the LOD value. Recovery values for samples spiked with oil standard containing Hg ranged from 95 to 105 %. The method is precise (inter‐day and intra‐day RSD<4 % for n=3) as well as the SPGE sensors (RSD=4.3 %, n=3), which were used continuously (around 100 analyses without replacement) under such oxidation media. The proposed method is feasible to be applied for on‐site determinations due to the portability of sensing and sample treatment approaches.

Antitumoural Sulphur and Selenium Heteroaryl Compounds: Thermal Characterization and Stability Evaluation.

The physicochemical properties of a compound play a crucial role in the cancer development process. In this context, polymorphism can become an important obstacle for the pharmaceutical industry because it frequently leads to the loss of therapeutic effectiveness of some drugs. Stability under manufacturing conditions is also critical to ensure no undesired degradations or transformations occur. In this study, the thermal behaviour of 40 derivatives of a series of sulphur and selenium heteroaryl compounds with potential antitumoural activity were studied. In addition, the most promising cytotoxic derivatives were analysed by a combination of differential scanning calorimetry, X-ray diffraction and thermogravimetric techniques in order to investigate their polymorphism and thermal stability. Moreover, stability under acid, alkaline and oxidative media was tested. Degradation under stress conditions as well as the presence of polymorphism was found for the compounds VA6E and VA7J, which might present a hurdle to carrying on with formulation. On the contrary, these obstacles were not found for derivative VA4J.

Facile and low cost oxidative conversion of MoS2 in α-MoO3: Synthesis, characterization and application

This study describes a facile low cost route to synthesize the α-MoO3 through a conversion of the precursor MoS2 in oxidant media. The structure and morphology of the α-MoO3 were studied by high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results show that α-MoO3 was obtained with reduced size, high purity, strongly-preferred orientation and structural defects, which ensures versatility and multifunctionality to this sample. For the purpose of applications, α-MoO3 was successfully employed in inverted organic solar cells devices as a possible alternative to the PEDOT:PSS in the hole transportation layer.

Reduced Graphene Oxide Membranes for Ultrafast Organic Solvent Nanofiltration.

Solvated reduced graphene oxide (S-rGO) membranes are stable in organic solvents, and strong acidic, alkaline, or oxidative media. They show high rejections to small molecules with charges the same as that of S-rGO coatings or neutral molecules larger than 3.4 nm, while retaining their high permeances to organic solvents.

The Influence of Oxidizing Medium on Structure, Mechanical Properties, and Breakage Pattern of Oxide Films of Zr—1% Nb Alloy under Conditions Simulating Oxidizing Media of WWER and PWR Reactors

This article investigates into the structure, phase composition, mechanical properties, and breakage pattern of oxide films formed on the surface of Zr—1% Nb alloy after corrosion tests in autoclave in water, steam, and water with lithium. Oxidation in water with lithium promotes formation of oxide films with a thickness of more than 100 μm, and, after oxidation in water or steam, the thickness is 5–15 μm. Upon oxidation in water, oxide films are generated with laminar structure: in the substrate, the grains are extended with the thickness of ~80 nm, near film surface the grains are equiaxial with the diameter of ~30 nm. After holding of the specimens in steam the oxide films are comprised mainly extended grains with the thickness of ~95 nm with a minor amount of equiaxial grains, 10%, with a diameter of ~30 nm, after oxidation in water with lithium the mixture of equiaxial and weakly extended nanograins is observed in the film structure. Upon loading of specimens with the structure of equiaxial and weakly extended grains the oxide films are broken due to generation of transversal cracks propagating to basic metal. The oxide films with laminar structure oxidized in water are broken due to exfoliation along the interface between the layers of extended and equiaxial grains. Breakage of films with the structure of equiaxial and weakly extended grains starts at the stage of elastic deformation at a stress of 300 MPa. The highest breakage stresses of 1150 MPa are characteristic for alloy specimens oxidized in steam. Breakage of films with laminar structure after oxidation in water occurs at average stresses of 798 MPa. The cohesive/adhesive strengths of films oxidized in water and steam are nearly the same. In thick alloys, oxide films oxidized in water with lithium, substrate does not open even at loading of 100 N. According to data of Raman spectroscopy, oxide film is mainly comprised of monoclinic phase of zirconium oxide; however, after oxidation in steam at the metal—film interface, a barrier layer of tetragonal phase of zirconium dioxide has been detected that prevents accelerated oxidation.

Thermal stability of meso-substituted metal corroles in inert and oxidative media

The thermal stability of 5,10,15-triphenylcorrole as the simplest representative of meso-substituted corroles and its complexes with d-metals (Cu3+, Mn3+, Mn4+, Co3+, Co4+, and Zn2+) is studied for the first time via thermogravimetry in oxidizing and inert atmospheres. It is shown that corroles, both as free ligands and in the form of metal complexes, are less thermally stable than porphyrins with a similar structure. It is found that if the free ligands of porphyrins are thermally more stable with respect to thermal oxidation than d-metal complexes, the thermal stability of metal corroles can be both lower and higher than those of free ligands. It is concluded that the order of thermal stability of compounds MnCor < CoCor < H3Cor < ZnCorH < CuCor is reversed upon moving from an oxidizing to an inert medium. It is shown that corroles complexes with many d-metals (Co, Mn, and others) readily participate in extracoordination reactions with electron-donating solvents, e.g., DMF, as is indicated by spectrophotometry and thermogravimetry.

Printed circuit board recycling: Physical processing and copper extraction by selective leaching

Global generation of waste electrical and electronic equipment (WEEE) is about 40 million tons per year. Constant increase in WEEE generation added to international legislations has improved the development of processes for materials recovery and sustainability of electrical and electronic industry. This paper describes a new hydrometallurgical route (leaching process) to recycle printed circuit boards (PCBs) from printers to recover copper. Methodology included PCBs characterization and a combined route of physical and hydrometallurgical processing. Magnetic separation, acid digestion and chemical analysis by ICP-OES were performed. On leaching process were used two stages: the first one in a sulfuric media and the second in an oxidant media. The results showed that the PCBs composition was 74.6wt.% of non-magnetic material and 25.4wt.% of magnetic one. The metallic fraction corresponded to 44.0wt.%, the polymeric to 28.5wt.% and the ceramic to 27.5wt.%. The main metal was copper and its initial content was 32.5wt.%. On sulfuric leaching 90wt.% of Al, 40wt.% of Zn and 8.6wt.% of Sn were extracted, whereas on oxidant leaching tests the extraction percentage of Cu was 100wt.%, of Zn 60wt.% and of Al 10wt.%. At the end of the hydrometallurgical processing was obtained 100% of copper extraction and the recovery factor was 98.46%, which corresponds to a 32kg of Cu in 100kg of PCB.

Magnetic Switching Behavior of Granular Perpendicular Magnetic Media With Different Lateral and Vertical Exchange Coupling

The magnetic switching behavior was measured for granular oxide media containing an exchange control layer (ECL). Investigations of the switching behavior show that the initial minor loop slope represents the degree of incoherent switching in the film. Multilayered granular oxide media with different inter-granular coupling in both lateral and vertical directions, is prepared by varying the oxide grain isolation and ECL thickness. The switching behavior of well isolated oxide grains strongly depends on the thermal stability of the switching segments through the ECL layer. The oxide grains with higher thermal stability vertically decouple at thinner ECL, resulting in a stronger incoherency of switching. In addition, the increase of lateral exchange coupling between oxide grains reduces the vertical decoupling at given ECL condition. For media with a smaller cluster size, the ECL magnetization and thickness has a more pronounced effect on the switching, indicating that fabrication of well isolated grains is important to optimize the media switching mode.

Structural Analysis of Single Wall Carbon Nanotubes Exposed to Oxidation and Reduction Conditions in the Course of Gamma Irradiation

Single wall carbon nanotubes (SWCNTs) were exposed to gamma irradiation in oxidative (H2O, NH4OH) and reductive (H2O and NH4OH both mixed with isopropyl alcohol) media. The structure has been investigated with microscopic (atomic force and transmission electron microscopy), spectroscopic (Raman, X-ray photoelectron, and FTIR spectroscopy) techniques, and by thermogravimetric analysis. Reductive media offer the possibility for green chemistry reduction of SWCNTs: after gamma irradiation, SWCNTs lose C–O bonds. Furthermore, irradiation in these media increases the fraction of sp2 hybridized carbon atoms in structure of SWCNTs and prevents their amorphization. The presence of isopropyl alcohol in reductive media contributed to the preservation of structure’s unity. On the other hand, the most effective procedure is the one that occurs in oxidative media and yields in debundled, cut, and annihilated carbon nanotubes. The smaller diameter and the metallic ones are the most affected.