Aqueous Matrix Research Articles

Construction of a photo-assisted peroxymonosulfate activation system comprised of iron phthalocyanine/O-doped carbon nitride for efficient tetracycline removal

The integration of peroxymonosulfate (PMS) activation and photocatalysis is an effective advanced oxidation technology for the degradation of water pollutants. In this study, iron phthalocyanine (FePc) is successfully loaded onto O-doped porous carbon nitride (OCN) forming a catalyst working in photo-assisted PMS activation. OCN is a metal-free light absorber with strong visible light absorption, while FePc could serve as a photosensitizer and PMS activator. At the same time, the construction of FePc/OCN heterojunction can form the strong internal electric field for charge migration between FePc and OCN. As a result, complete tetracycline (TC) removal within 30 min can be achieved over optimal FePc/OCN catalyst in the presence of light and PMS. Systematic controlled experiments were also carried out to reveal the effect of pH, anion, and aqueous matrix. Cyclic stability test and Fe leaching experiments indicate that the synthesized FePc/OCN is relatively stable and shows the potential in practical application. Furthermore, a comprehensive investigation was conducted on the reactive species generated during the reaction process as well as the degradation pathways of the target pollutants. This work aims to provide new insights into the design of efficient catalysts for photo-assisted PMS activation.

Recovery of Isoamyl Alcohol by Graphene Oxide Immobilized Membrane and Air-Sparged Membrane Distillation.

Isoamyl alcohol is an important biomass fermentation product that can be used as a gasoline surrogate, jet fuel precursor, and platform molecule for the synthesis of fine chemicals and pharmaceuticals. This study reports on the use of graphene oxide immobilized membra (GOIMs) for the recovery of isoamyl alcohol from an aqueous matrix. The separation was performed using air-sparged membrane distillation (ASMD). In contrast to a conventional PTFE membrane, which exhibited minimal separation, preferential adsorption on graphene oxide within GOIMs resulted in highly selective isoamyl alcohol separation. The separation factor reached 6.7, along with a flux as high as 1.12 kg/m2 h. Notably, the overall mass transfer coefficients indicated improvements with a GOIM. Optimization via response surfaces showed curvature effects for the separation factor due to the interaction effects. An empirical model was generated based on regression equations to predict the flux and separation factor. This study demonstrates the potential of GOIMs and ASMD for the efficient recovery of higher alcohols from aqueous solutions, highlighting the practical applications of these techniques for the production of biofuels and bioproducts.

Analysis of VOCs in Liquids through Vaporization in a Tubular Oven Monitored by Chemical Ionization Mass Spectrometry.

The analysis of chemical compounds present at trace levels in liquids is important not only for environmental measurements but also, for example, in the health sector. The reference technique for the analysis of Volatile Organic Compounds (VOCs) in liquids is GC, which is difficult to use with an aqueous matrix. In this work, we present an alternative technique to GC to analyze VOCs in water. A tubular oven is used to completely vaporize the liquid sample deposited on a gauze. The oven is heated in the presence of a dinitrogen flow, and the gas is analyzed at the exit of the oven by a chemical ionization mass spectrometer developed in our laboratory. It is a low magnetic field Fourier Transform Ion Cyclotron Resonance (FT-ICR) optimized for real-time analysis. The Proton Transfer Reaction (PTR) used during the Chemical Ionization event results in the selective ionization of the VOCs present in the gas phase. The optimization of the desorption conditions is described for the main operating parameters: temperature ramp, liquid quantity, and nitrogen flow. Their influence is studied using a 100 ppmv aqueous toluene solution. The analytical method is then tested on a mixture of seven VOCs.

Amorphization of natural ilmenite for production of a potential porous adsorbent towards crystal violet dye removal from aqueous environment

In this work, amorphization of ilmenite mineral was obtained by solid NaOH alkaline fusion at 550 oC. The material was tested as an adsorbent towards crystal violet (CV) removal from an aqueous matrix. Several techniques, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and N2 adsorption/desorption isotherms (BET) were used to characterize the material, and revealed an amorphous structure with superior surface area (88.84 m² g-1) compared to raw sample (5.90 m² g-1). These intrinsic characteristics resulted in a satisfactory adsorption capacity, reaching 133 mg g-1 at a temperature of 328 K. Kinetic studies on the adsorption process indicated that the equilibrium condition was reached within 50 min, being well represented by the Avrami model. The thermodynamic study revealed that the CV adsorption onto ilmenite is spontaneous, endothermic, and favorable. The amorphized material maintains the same adsorptive performance after three reuse cycles. Therefore, the amorphization route proposed in this work was satisfactory for producing a porous adsorbent from the ilmenite mineral, with potential use for wastewater treatment.

Reusable porous chromium- zinc oxide nano-sheets for efficient detoxification of xenobiotics through integrated advanced oxidation water clean-up process

An integrated approach of acoustic, ultraviolet, and sunlight-driven Advanced Oxidation Process (AOP) is an excellent choice in the quest for a water-cleaning process. This research delves into the realization of chromium-doped zinc oxide (Cr/ZnO) nanopores as a low energy, eco-friendly, efficient, and exhibiting stable photocatalysis for the AOP process. Ultrasonic-aided co-precipitation technique was used for the synthesis of porous Cr-ZnO nanostructures. X-ray diffraction patterns and FTIR spectra of the synthesized samples revealed that chromium ions were effectively intruded into the ZnO lattice. Tauc's equation and Kubella Munk plots have explored that the incorporation of Cr dopants in ZnO reduces the optical band energy. The formation of porous structures was evinced in SEM, TEM, HRTEM, and BET studies. The presence of abundant mesoporous structures was confirmed by the adsorption/desorption isotherms of type IV hysteresis. The antimicrobial efficacy of Cr-ZnO against aqueous bacteria, Staphylococcus aureus, and Escherichia coli was comparatively as effective as the control. The integrated AOP approach enhances the electron trapping characteristics of nanoporous Cr-ZnO catalysts to generate self-sustained in-situ reactive oxygen species on the aqueous matrix. In the current research, methylene orange and nitro phenol were detoxified up to 99 % and 98.2 %, and their half-life degradation rate constant was 22 min and 26 min, respectively. The total organic contaminants (TOC) test on the resultant treated water has confirmed the effective detoxification of xenobiotic molecules and the possibility of reusing the treated water. The ecotoxicology research using treated water on flora and primary aquatic microfauna has supported the possibility of practical utilization of Cr-ZnO in harmless environmental adaptation in the foreseeable future.

REMOVAL OF DRUGS FROM AQUEOUS MATRIXES USING A REVERSE OSMOSIS MEMBRANE

Pollution of water bodies by micropollutants is a problem of growing concern, especially regarding contamination with drug residues and metabolites. The presence of these substances in surface waters is related to deleterious consequences for the population and the environment. The incorrect disposal of drug residues and the low efficiency of conventional water treatment methods require the use of alternative methods, such as the use of membrane separation processes for the treatment of effluents. The present study aimed to evaluate the efficiency of a reverse osmosis membrane for the removal of ibuprofen and diclofenac sodium from an aqueous matrix. For this, permeation tests were performed with aqueous solutions of diclofenac and ibuprofen at a concentration of 10 mg∙L-1, alone and together. The hydraulic permeability of the membrane and the drug rejection efficiency were evaluated. The presence of drugs in the solution had little influence on the hydraulic permeability of the membrane. The minimum removal efficiency of both substances was greater than 98.5 %, generating a permeate stream practically free of drugs, whether evaluated separately or in the same solution. These results indicate the operational robustness of the membrane since neither the permeability nor the rejection were altered by the fact that we have the two drugs combined, in addition to demonstrating the potential use of reverse osmosis as a treatment method for the removal of residues and traces of drugs and other difficult-to-treat organic substances in aqueous matrices.

Solar-assisted oxidation of organochlorine pesticides in groundwater using persulfate and ferrioxalate

The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes qw= 1.12·10−7 E cm−2s−1 and in compound parabolic collectors with solar light (qw≈10−7 E cm−2s−1) for 390 min. The effect of activator dosage (18–125 μM ferrioxalate) and persulfate concentration (520–2600 μM) on hexachlorocyclohexane conversion and oxalate and oxidant consumption was analyzed. Conversion of about 95% of β isomer was achieved at 390 min using 1300 μM of initial persulfate and 63 μM of Fe3+ concentration despite this β isomer being the most recalcitrant to oxidation (XHexachlorocyclohexanes=0.98). Dechlorination above 80% was achieved under these conditions, analyzing the chlorides released into the water.The influence of chloride and bicarbonate on hexachlorocyclohexanes degradation was analyzed in milli-Q water and in groundwater. Hexachlorocyclohexane conversion at 390 min decreases from 98% to 83, 75 and 65% in the presence of chloride, bicarbonate or groundwater, respectively. Results obtained with compound parabolic collectors and solar light using 2600 μM Na2S2O8 and 63 μM Fe for removing hexachlorocyclohexanes agreed with those from the solar simulator reactor, supporting using solar light to activate persulfate for sustainable abatement of persistent organic pollutants in aqueous matrixes.

Quantification of Antiviral Drug Tenofovir (TFV) by Surface-Enhanced Raman Spectroscopy (SERS) Using Cumulative Distribution Functions (CDFs).

Surface-enhanced Raman spectroscopy (SERS) is an ultrasensitive spectroscopic technique that generates signal-enhanced fingerprint vibrational spectra of small molecules. However, without rigorous control of SERS substrate active sites, geometry, surface area, or surface functionality, SERS is notoriously irreproducible, complicating the consistent quantitative analysis of small molecules. While evaporatively prepared samples yield significant SERS enhancement resulting in lower detection limits, the distribution of these enhancements along the SERS surface is inherently stochastic. Acquiring spatially resolved SERS spectra of these dried surfaces, we have shown that this enhancement is governed by a power law as a function of analyte concentration. Consequently, by definition, there is no true mean of SERS enhancement, requiring an alternative approach to achieve reproducible quantitative results. In this study, we introduce a new method of analysis of SERS data using a cumulative distribution function (CDF). The antiviral drug tenofovir (TFV) in an aqueous matrix was quantified down to a clinically relevant concentration of 25 ng/mL using hydroxylamine-reduced silver colloids evaporated to dryness. The data presented in this study provide a rationale for the benefits of combining a novel statistical approach using CDFs with simple and inexpensive experimental techniques to increase the precision, accuracy, and analytical sensitivity of aqueous TFV quantification by SERS. TFV calibration curves generated using CDF analysis showed higher analytical sensitivity (in the form of a normalized calibration curve average slope increase of 0.25) compared to traditional SERS intensity calculations. A second aliquot of nanoparticles and analyte dried on the SERS surface followed by CDF analysis showed further analytical sensitivity with a normalized calibration curve slope increase of 0.23 and decreased variation among replicates represented by an average standard deviation decrease of 0.02 with a second aliquot. The quantitative analysis of SERS data using CDFs presented here shows promise to be a reproducible method for quantitative analysis of SERS data, a significant step toward implementing SERS as an analytical method in clinical and industrial settings.

Development of a column switching for direct online enrichment and separation of polar and nonpolar analytes from aqueous matrices

Trace substances in surface waters may threaten health and pose a risk for the aquatic environment. Moreover, separation and detection by instrumental analysis is challenging due to the low concentration and the wide range of polarities. Separation of polar and nonpolar analytes can be achieved by using stationary phases with different selectivity. Lower limits of detection of trace substances can be obtained by offline enrichment on solid phase materials. However, these practices require substantial effort and are time consuming and costly. Therefore, in this study, a column switching was developed to enrich and separate both polar and nonpolar analytes by an on-column large volume injection of aqueous samples. The column switching can significantly reduce the effort and time for analyzing trace substances without compromising on separation and detection. A reversed phase (RP) column is used to trap the nonpolar analytes. The polar analytes are enriched on a porous graphitized carbon column (PGC) coupled serially behind the RP column. A novel valve switching system is implemented to enable elution of the nonpolar analytes from the RP column and, subsequently, elution of polar analytes from the PGC column and separation on a hydrophilic interaction liquid chromatography (HILIC) column. To enable separation of polar analytes dissolved in an aqueous matrix by HILIC, the water plug that is flushed from the PGC column is diluted by dosing organic solvent directly upstream of the HILIC column. The developed method was tested by applying target analysis and non-target screening, highlighting the advantage to effectively separate and detect both polar and nonpolar compounds in a single chromatographic run. In the target analysis, the analytes, with a logD at pH 3 ranging from -2.8 to + 4.5, could be enriched and separated. Besides the 965 features in the RP phase, 572 features from real wastewater were observed in the HILIC phase which would otherwise elute in the void time in conventional one-dimensional RP methods.

Comparison of plastic pollution between waters and sediments in four Po River tributaries (Northern Italy)

The monitoring of plastic contamination in freshwaters is still pioneering in comparison with marine environments, and few studies analyzed the distribution of these pollutants in both aqueous and bottom compartments of continental waters. Therefore, the aim of this study was the comparison of plastic pollution in both waters and sediments of four Po River tributaries (Ticino, Adda, Oglio and Mincio Rivers), which outflow from the main Italian sub-alpine Lakes, in order to establish the strengths and weaknesses of both matrices. The main results pointed out a heterogeneous plastic contamination, with the lowest values in Ticino (0.9 ± 0.5 plastics/m3 in waters and 6.8 ± 4.5 plastics/kg dry weight - d.w. - in sediments) and the highest in Mincio (62.9 ± 53.9 plastics/m3 in waters and 26.5 ± 13.3 plastics/kg d.w in sediments), highlighting a plastic amount in sediments four times higher than waters. Plastic pollution, mainly due to microplastics, was associated principally to a domestic input in both waters and sediments of Ticino and Adda Rivers, as well as in sediments of Oglio, while an industrial pollution was found in waters and sediments of Mincio and Oglio waters. Our data clearly highlighted as the monitoring of both matrices provide complementary information for a holistic risk assessment of these emerging contaminants in freshwaters: the aqueous matrix provides an instantaneous picture of contamination, while sediments the history of pollution.

Ultraviolet germicidal irradiation: A prediction model to estimate UV-C-induced infectivity loss in single-strand RNA viruses

Ultraviolet germicidal irradiation (UVGI) disinfection technology is effective in inactivating microorganisms. However, its performance can vary against different microorganisms due to their diverse structural and genomic features. Thus, rapid predictions of UV (254 nm) inactivation kinetics are essential, particularly for highly infectious emerging pathogens, such as SARS-CoV-2, during the extemporary COVID-19 pandemic. In this study, aiming at single-strand RNA (ssRNA) viruses, an improved genomic model was introduced to predict the UV inactivation kinetics of viral genomes using genome sequence data. First, the overall virus infectivity loss in an aqueous matrix was estimated as the sum of damage to both the entire genome and the protein capsid. Then, the “UV rate constant ratio of aerosol and liquid” was used to convert the UV rate constant for viruses in a liquid-based matrix to an airborne state. The prediction model underwent both quantitative and qualitative validation using experimental data from this study and the literature. Finally, with the goal of mitigating potential airborne transmission of ssRNA viruses in indoor environments, this paper summarizes existing in-duct UVGI system designs and evaluates their germicidal performance. The prediction model may serve as a preliminary tool to assess the effectiveness of a UVGI system for emerging or unculturable viruses or to estimate the required UV dose when designing such a system.

Ozone-treated activated alumina as an alternative adsorbent to remove fluoride from water: Conventional and Bayesian approaches to evaluate the isotherms, kinetics, and thermodynamics

Activated alumina (AA) is a widespread adsorbent for removing fluoride from water. Despite its high affinity and selectivity for fluoride, its use has some limitations. In addition to the low adsorption capacity of this adsorbent and the long time required to reach equilibrium, the pH of the aqueous matrix must be less than 6.0 for AA to achieve high levels of fluoride removal. This study investigated the potential application of ozone-treated activated alumina (OAA), a new adsorbent material obtained by the ozonation of AA, to remove fluoride from water in a wide pH range. The performance of OAA on fluoride adsorption under different conditions of pH and dosage (g/L) was evaluated using a central composite rotational design (CCRD). As a result, using an adsorbent dosage of 4.35 g/L, OAA achieved high fluoride rates (>94%) over a wide range of pH values (4−8). The Minimum Square Method (MSM) and Monte Carlo Markov Chain (MCMC) methodologies obtained kinetic and equilibrium parameters. The Liu model was the most suitable isotherm model, which obtained a qm of 15.80 mg/g. Among the kinetic models, the general order model was the one that best fitted experimental data. Through thermodynamic analysis, the nature of fluoride adsorption on OAA was found to be endothermic and spontaneous. The fluoride removal efficiency of OAA (98.7%) was higher than AA (46.7%) at the same experimental conditions, showing the modification of AA by using the ozonation process was effective. Finally, the influence of co-existing ions (Cl-, SO42-, NO3-) and the regeneration and reuse of OAA were also evaluated.

Removal of Pharmaceuticals from an Aqueous Matrix by Adsorption on Metal–Organic Framework MIL-100(Cr)

Removal of Pharmaceuticals from an Aqueous Matrix by Adsorption on Metal–Organic Framework MIL-100(Cr)

Effect of tannic acid-OSA starch complexation on the binding capacity and release of aldehydes off-flavor in aqueous matrix.

In order to further clarify the regulation of tannic acid on the off-flavor in starch-based algal oil emulsions, the effect of different starch matrix (OSA starch and OSA starch-tannic acid complex) on the release capacities of aldehydes (pentanal, hexanal, heptanal, nonanal) were investigated. The adsorption and retention ability, thermodynamic parameters, and hydrophobicity of aldehydes in the starch matrix were analyzed. Nonanal exhibited the strongest adsorption ability (65.01%-85.69%) with the starch matrix, followed by heptanal, hexanal, and pentanal, which accounted for the structures of aldehydes. Furthermore, aldehydes had a higher affinity with complex (16.33%-83.67%) than OSA starch (9.70%-66.71%) because the tannic acid altered the structure of OSA starch. Isothermal titration calorimetry suggested that the interaction between the starch matrix and aldehydes was an entropy-driven spontaneous endothermic reaction, and hydrophobic interactions were the predominant driving forces. Altogether, these results lay a theoretical foundation for facilitating the regulation of flavor in starch foods.

Application of green-synthesized cadmium oxide nanofibers and cadmium oxide/graphene nanosheet nanocomposites as alternative and efficient photocatalysts for methylene blue removal from aqueous matrix.

For the first time, cadmium oxide (CdO) nanofibers (NFs) and graphene nanosheet (GNS)-doped CdO nanocomposites (NCs) have been synthesized by a simple green route using green tea (Camellia sinensis) extract, for subsequent application as photocatalysts for methylene blue (MB) removal from an aqueous matrix. In addition, the materials were tested as working electrodes for supercapacitors. The prepared samples were analyzed by FESEM, UV-Vis spectroscopy, FTIR, and X-ray diffraction (XRD). FESEM revealed that the obtained NPs and NCs show fiber-shaped nanostructure. FTIR confirmed the presence of biomolecules on CdO and carbon compounds on CdO/GNS, while XRD exhibited the cubic crystalline structure of obtained NPs and NCs. The Rietveld refinement using XRD data was performed to ascertain the crystallographic characteristics of the produced samples and look into lattice imperfections. UV-Vis spectroscopy evaluated the optical bandgap energies of CdO and CdO/GNS NCs. The CdO/GNS NCs demonstrated a fast cleavage of the dye molecule under UV irradiation, resulting in 97% removal in 120 min. In addition, CdO/GNS NCs showed remarkable chemical stability as an electrode material, with a high specific capacitance of 231 F g-1 at a scan rate of 25 mV s-1. These observed NCs characteristics are higher when compared to pristine CdO NPs. Finally, we found that the investigated NCs showed enhanced multifunctional properties, such as photocatalytic and supercapacitor characteristics, which can be useful in practical applications.

UiO-66 octahedrons for adsorptive removal of direct blue-6: process optimization, interaction mechanism, and phytotoxicity assessment.

The materials for water treatment have been evolving in multitude of dimensions, indicating the importance of water reuse and increasing level of water pollution around the globe. Among the various materials that are utilized in wastewater treatment, the material that has attracted the research community for the past decades is the metal organic framework (MOF). In this work one of the water stable and microporous MOF, UiO-66, and its aminated version has been employed to adsorb an anionic azo dye, direct blue-6 (DB-6), from the aqueous matrix. Performance of both the MOFs was compared to know the efficiency under varying solution conditions. The optimized parameters for DB-6 adsorption by UiO-66 was performed using response surface methodology. This numerical optimization was further extended with canonical and ridge analysis. Under optimal conditions, the materials were exhibiting a good adsorption capacity of 754.4mg/g. The materials were analyzed in terms of morphology, crystallinity, thermal stability, and surface area using instruments like X-ray diffraction, electron microscopy, thermogravimetric analysis, and BET surface area analysis. The mechanism of interaction between UiO-66 and DB-6 molecule was elucidated with the help of XPS analysis which helps to know the main interacting group of UiO-66. This study was concluded with a phytotoxicity analysis of DB-6 and the antioxidant system of Vigna radiata assessed using pre and post adsorbed water.

Activation of PMS degradation of chlorotriazine herbicides (atrazine and simazine) by MIL101-derived Fe/Co@C under high salinity conditions

In this work, a carbon-based catalyst Fe/Co@C with MOF as a self-sacrificing template was prepared by high-temperature roasting of FeCo-MIL101, which was applied to activate PMS for the degradation of chlorotriazine herbicides (ATZ and SIM) showing excellent performance. Characterization analysis revealed that Fe/Co@C possesses a certain graphene structure and has a saturation magnetization rate of 0.87 emu/g, which can be separated from the solution easily and quickly. The degradation of ATZ and SIM was enhanced by introducing chloride ions into the system, and 100 mmol/L Cl- could lead to the complete removal of ATZ and SIM in 6 min, while improving the interfacial electron transfer of Fe/Co@C/PMS. In combination with quenching experiments, ESR test results and DFT calculations, two important roles of chlorine radicals in the reaction are proposed: (1) direct electron transfer and (2) indirect promotion of 1O2 generation through the production of HOCl. In addition, the testing of the influencing factors of the catalyst in the system (catalyst dosing, PMS dosing, pH, temperature), the testing of coexisting anions in the aqueous matrix, and the reusability all showed satisfactory performance. Finally, the degradation mechanisms of ATZ and SIM were proposed in combination with GC–MS determination of contaminant intermediates and analysis of their toxicity.

Synthesis, characterization, functional testing and ageing analysis of bifunctional Zn-air battery GDEs, based on α-MnO2 nanowires and Ni/NiO nanoparticle electrocatalysts

Electrically rechargeable alkaline zinc air batteries (RZAB) – currently still at the R&D stage –, have great potential for stationary, as well as prospectively mobile, electrochemical energy storage applications. Their chief appeal is that they are made of abundant, environmentally friendly, intrinsically safe, and cheap materials, with established recycling concepts and auspicious life-cycle costs. One of the key weak points of present-generation RZAB programs is the air gas-diffusion electrode (GDE). In fact, on the one hand, GDE fabrication and testing are generally based on poorly understood protocols, and, on the other hand, performance is challenged by efficiency and durability issues. This work is centred on the fabrication of a novel bifunctional GDE for the air side of RZABs, on the assessment of its electrochemical performance and on the identification of factors impacting its efficiency and durability. The electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are α-MnO2 nanowires and Ni/NiO nanoparticles, respectively. The composition of the active layer was optimized with rotating ring-disc electrode (RRDE) electrocatalysts tests. The GDEs were fabricated by spray-coating an ink, formulated with the electrocatalysts and the PTFE binder in an aqueous matrix. Fabrication and functional performance of GDEs – in pristine form and after ageing under realistic RZAB conditions – are rationalized on the basis of Scanning Electron Microscopy (SEM), Scanning Transmission X-ray SpectroMicroscopy (STXSM) at the Mn l-edge and Transmission Electron Microscopy (TEM) analyses. Imaging and spectral imaging disclosed the morphological and chemical-state evolution, brought about by electrochemical cycling. Special attention was devoted to the understanding of the role played by the presence of zincate in the electrolyte on the performance and ageing of the reversible air electrodes.

Detection and quantification of antiviral drug tenofovir using silver nanoparticles and surface enhanced Raman spectroscopy (SERS) with spatially resolved hotspot selection

This study introduces a convenient and ultra-sensitive method of detection and quantification of the antiviral drug, tenofovir (TFV), by surface-enhanced Raman spectroscopy (SERS). Novel spatially resolved instrumentation for spectral acquisition and subsequent statistical analysis for hot spot selection was developed for convenient quantification of TFV in an aqueous matrix. Methods of statistical analysis include the use of partial least squares (PLS) regression vector analysis and spectral ranking by quality indices computed using CHAOS theory. Hydroxylamine-reduced Ag colloidal nanoparticles evaporated to dryness on an aluminum well-plate were used as the SERS substrate. To our knowledge, quantification of TFV down to 25 ng/mL by SERS, comprising clinically relevant concentrations, has not been previously reported. Furthermore, in this work we propose a novel method of quantification of aqueous TFV standards by SERS using statistical treatment of data by PLS and CHAOS theory. Based on these data, we propose future studies to develop a method of TFV detection and quantification in biological samples, beneficial to clinicians for rapid assessment of drug adherence during the treatment and prevention of viral diseases.

Personalised modelling of clinical heterogeneity between medium-chain acyl-CoA dehydrogenase patients

BackgroundMonogenetic inborn errors of metabolism cause a wide phenotypic heterogeneity that may even differ between family members carrying the same genetic variant. Computational modelling of metabolic networks may identify putative sources of this inter-patient heterogeneity. Here, we mainly focus on medium-chain acyl-CoA dehydrogenase deficiency (MCADD), the most common inborn error of the mitochondrial fatty acid oxidation (mFAO). It is an enigma why some MCADD patients—if untreated—are at risk to develop severe metabolic decompensations, whereas others remain asymptomatic throughout life. We hypothesised that an ability to maintain an increased free mitochondrial CoA (CoASH) and pathway flux might distinguish asymptomatic from symptomatic patients.ResultsWe built and experimentally validated, for the first time, a kinetic model of the human liver mFAO. Metabolites were partitioned according to their water solubility between the bulk aqueous matrix and the inner membrane. Enzymes are also either membrane-bound or in the matrix. This metabolite partitioning is a novel model attribute and improved predictions. MCADD substantially reduced pathway flux and CoASH, the latter due to the sequestration of CoA as medium-chain acyl-CoA esters. Analysis of urine from MCADD patients obtained during a metabolic decompensation showed an accumulation of medium- and short-chain acylcarnitines, just like the acyl-CoA pool in the MCADD model. The model suggested some rescues that increased flux and CoASH, notably increasing short-chain acyl-CoA dehydrogenase (SCAD) levels. Proteome analysis of MCADD patient-derived fibroblasts indeed revealed elevated levels of SCAD in a patient with a clinically asymptomatic state. This is a rescue for MCADD that has not been explored before. Personalised models based on these proteomics data confirmed an increased pathway flux and CoASH in the model of an asymptomatic patient compared to those of symptomatic MCADD patients.ConclusionsWe present a detailed, validated kinetic model of mFAO in human liver, with solubility-dependent metabolite partitioning. Personalised modelling of individual patients provides a novel explanation for phenotypic heterogeneity among MCADD patients. Further development of personalised metabolic models is a promising direction to improve individualised risk assessment, management and monitoring for inborn errors of metabolism.