Study of humic-like substances of dissolved organic matter using size exclusion chromatography and chemometrics.

The study of dissolved organic matter (DOM) presents a significant challenge for environmental analyses and the monitoring of wastewater treatment plants (WWTPs). This is particularly true for the tracking of recalcitrant to biodegradation dissolved organic matter (rDOM) compounds, which is generated during the thermal pretreatment of sludge. This study aims to develop analytical and chemometric methods to differentiate melanoidins from humic acids (HAs), two components of rDOM that require monitoring at various stages of wastewater treatment processes due to their distinct biological effects. The developed method implements the separation of macromolecules through ultra-high-performance liquid chromatography size-exclusion chromatography (U-HPLC SEC) followed by online UV and fluorescence detection. UV detection was performed at 210, 254, and 280 nm, and fluorescence detection at six excitation/emission pairs: 230/355 nm, 270/355 nm, 240/440 nm, 270/500 nm, 330/425 nm, and 390/500 nm. Chromatograms obtained for each sample from these nine detection modes were integrated and separated into four molecular fractions: >40 kDa, 20-40 kDa, 10-20 kDa, and <10 kDa. To enhance analytical resolution and normalize the data, ratios were calculated from the areas of chromatographic peaks obtained for each detection mode. The results demonstrate the utility of these ratios in discriminating samples composed of HAs, melanoidins, and their mixtures, through principal component analysis (PCA). Low molecular weight fractions were found to be specific to melanoidins, while high molecular weight fractions were characteristic of HAs. For the detection modes specific to melanoidins, UV absorbance at 210, 254, and 280 nm were predominantly present in the numerators, with tryptophan-like fluorescence emissions in the denominators. Conversely, fluorescence emissions largely represented both numerators and denominators for HAs. This online method also enables the discrimination of pseudo-melanoidins, compounds revealing a nitrogen deficiency in their chemical structures.

Customizing Cerium Oxide Particle Synthesis with Hybrid Polyion Complex Templates for Enhanced Oxidation Performance in Photo-Fenton Processes.

Hybrid poly-ion complexes were synthesized through the complexation of a double hydrophilic copolymer with Ce(III) ions. These colloids act as reservoirs for cerium ions, enabling the synthesis of cerium-based Prussian blue nanoparticles with a cubic structure, a narrow size distribution around 100 nm, and good colloidal stability in water. Upon high-temperature calcination, these nanoparticles are transformed into a cerium/iron-based metal oxide catalyst (CeO2/Fe2O3). The resultant composite catalyst demonstrates superior performance in the photo-Fenton oxidation of methylene blue pollutants, achieving a conversion efficiency that rivals other metal-based oxides and cerium-based catalysts.

Iron-based hybrid polyionic complexes as chemical reservoirs for the pH-triggered synthesis of Prussian blue nanoparticles.

HYPOTHESIS: Hybrid polyion complexes (HPICs) obtained from the complexation in aqueous solution of a double hydrophilic block copolymer and metal ions can act as efficient precursors for the controlled synthesis of nanoparticles. In particular, the possibility to control the availability of metal ions by playing on the pH conditions is of special interest to obtain nanoparticles with controlled size and composition. EXPERIMENTS: HPICs based on Fe3+ ions were used to initiate the formation of Prussian blue (PB) nanoparticles in presence of potassium ferrocyanide in reaction media with varying pH values. FINDINGS: Complexed Fe3+ ions within HPICs can be easily released by adjusting the pH value either through the addition of a base/acid or by using a merocyanine photoacid. This allows to modulate the reactivity of Fe3+ ions with potassium ferrocyanide present in solution. As a result, PB nanoparticles with different structures (core, core-shell), composition and controlled size are obtained.

Copper-Based Hybrid Polyion Complexes for Fenton-Like Reactions.

An innovative strategy allowing the development of a new generation of easy-to-prepare and easy-to-use nano-sized catalysts with high tenability is presented. This strategy is based on the formation of hybrid polyion complexes (HPICs) from the complexation of copper with a block copolymer consisting of an ionizable complexing block and a neutral stabilizer block. These complexes have a well-defined structure and size with a hydrodynamic diameter around 29 nm. They are stable in aqueous solution over a pH range from 4 to 8 and are not sensitive to NaCl salt addition or dilution effects. As a proof-of-concept the degradation of naphthol blue black in water through the use of the Fenton or photo-Fenton reaction is studied. Their performances are comparable to a classical homogeneous reaction, whereas HPICs are easily recyclable by simple dialysis.

Analysis of the retention of tetracyclines on reversed-phase columns: Chemometrics, design of experiments and quantitative structure-property relationship (QSPR) study for interpretation and optimization.

In this study, design of experiments was applied for the analysis of 6 reversed phase U-HPLC columns used for the separation of four tetracyclines (TCs): tetracycline, doxycycline, chlortetracycline and oxytetracycline in different elution conditions. In a first part, a fractional factorial design (24-1) was used to study the influence of four chromatographic parameters: column temperature, pH, flow rate and composition of the mobile phase (i.e. nature of the solvent used as the organic modifier), on the quality of the separation, which was evaluated in terms of peak width and resolution between two pairs of TCs. This experimental design revealed that the nature of the solvent: acetonitrile (ACN) or methanol (MeOH), and the mobile phase flow rate were the two main factors actually having the most influence on the quality of the separation. Moreover, these two factors presented an antagonistic influence according to the response considered: peak width or peak resolution. In order to understand this behavior, a Doehlert design was performed in the second part. It consisted in modeling the evolution of responses as a function of the two main factors: nature of the composition of the mobile phase (mix of ACN and MeOH, from 100% ACN to 100% MeOH) and mobile phase flow rate (from 0.3 to 0.8 mL min-1). For all the reversed phase columns studied, an inversion of the elution order of TCs and an increase of the retention factors was observed according to the composition of the organic mixture at the end of the gradient. To understand the modification of the interactions implied in the various retention modes related to the selectivity of the organic solvents used, a quantitative structure-property relationship (QSPR) study was achieved. In this final study, the molecular descriptors of each TCs were connected to its retention factor.

Photochemical Degradation of the Anticancer Drug Bortezomib by V-UV/UV (185/254 nm) Investigated by (1)H NMR Fingerprinting: A Way to Follow Aromaticity Evolution.

We have investigated the removal of bortezomib, an anticancer drug prescribed in multiple myeloma, using the photochemical advanced oxidation process of V-UV/UV (185/254 nm). We used two complementary analytical techniques to follow the removal rate of bortezomib. Nuclear magnetic resonance (NMR) is a nonselective method requiring no prior knowledge of the structures of the byproducts and permits us to provide a spectral signature (fingerprinting approach). This untargeted method provides clues to the molecular structure changes and information on the degradation of the parent drug during the irradiation process. This holistic NMR approach could provide information for monitoring aromaticity evolution. We use liquid chromatography, coupled with high-resolution mass spectrometry (LC-MS), to correlate results obtained by (1)H NMR and for accurate identification of the byproducts, in order to understand the mechanistic degradation pathways of bortezomib. The results show that primary byproducts come from photoassisted deboronation of bortezomib at 254 nm. A secondary byproduct of pyrazinecarboxamide was also identified. We obtained a reliable correlation between these two analytical techniques.

Mechanistic pathways of the photolysis of paracetamol in aqueous solution: an example of photo-Fries rearrangement.

The mechanism of the photolysis of N-(4-hydroxyphenyl)ethanamide (paracetamol, PA), a widely prescribed analgesic and antipyretic drug, has been investigated in the absence and in the presence of oxygen. Identification of products and kinetic analyses were performed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) and by ultra-performance liquid chromatography with a diode array detector (UPLC-PDA). The results show that, under irradiation at 254 nm and independently of the presence of oxygen, the predominant reaction pathway is a photo-Fries rearrangement (PFR), yielding the PA isomer 2'-amino-5'-hydroxyacetophenone (PAI). This reaction occurs from the singlet excited state of the molecule and involves the migration of the acetyl group onto the aromatic ring in the ortho-position to the amine moiety. The formation of 4-aminophenol (4-AP) was observed as a minor competitive pathway. The quantum yield of PA consumption (Φ(-PA)) was determined to be 1.0(±0.1) × 10(-3) by chemical actinometry. As its concentration increases, the PFR product (PAI) competes with PA for light absorption and undergoes, in the presence of oxygen, a photooxygenation process leading to the formation of a peroxyester.

Degradation of 2,4-dihydroxibenzoic acid by vacuum UV process in aqueous solution: kinetic, identification of intermediates and reaction pathway.

2,4-Dihydroxybenzoic acid (2,4-DHBA) is found frequently as a pollutant in natural waters and represents a threat to water quality because it is a precursor to the formation of quinones which are highly toxic. The degradation of 2,4-DHBA using the vacuum UV photolysis of water has been investigated. Irradiation was carried out in an annular photoreactor equipped with a Xe-excimer lamp situated in the centre and emitting at 172 nm. The degradation kinetic followed a pseudo first order and the reaction has been found to be very heterogeneous, especially at low concentration. Impacts of oxygen or temperature have also been investigated but no effect has been shown. LC-MS and HPLC-UV combined with other analytical techniques allowed the identification of the formation of trihydroxybenzoïc acids and trihydroxybenzenes which underwent a ring opening, conducting to the formation of aliphatic products named α, ß, δ and γ. These products were in turn degraded successively into maleïc acid, malic and succinic acid, malonic acid, glyoxalic acid and oxalic acid before reaching the complete mineralization in about 180 min. The proposed reaction pathway has shown to be very different from the one observed for the TiO(2) photocatalysis which involves only holes (h(+)) without any formation of aromatic intermediates. The different behaviours of 2,4-DHBA towards the h(+) and HO make it a good probe to identify involved entities.

Hydrogen peroxide evolution during V-UV photolysis of water.

Hydrogen peroxide evolution during the vacuum-ultraviolet (V-UV, 172 nm) photolysis of water is considerably affected by the presence of oxalic acid (employed as a model water pollutant) and striking differences are observed in the absence and in the presence of dioxygen.