RESUMO

This study unveils a novel role of bare graphite as a catalyst in glycerol electrooxidation and hydrogen evolution reactions, challenging the prevailing notion that current collectors employed in electrolyzers are inert. Half-cell experiments elucidate the feasibility of glycerol oxidation and hydrogen production on bulk graphite electrodes at potentials exceeding 1.7 V. The investigation of varying glycerol concentrations (0.05 to 1.5 mol L-1) highlights a concentration-dependent competition between glycerol electrooxidation and oxygen evolution reactions. Employing an H-type glycerol electrolyzer, polarization curves reveal significant activation polarization attributed to the low electroactivity of the anode. Glycerol electrolysis at different concentrations yields diverse product mixtures, including formate, glycolate, glycerate, and lactate at the anode, with concurrent hydrogen generation at the cathode. The anolyte composition changes with glycerol concentration, resulting in less-oxidized compounds at higher concentrations and more oxidized compounds at lower concentrations. The cell voltage also influences the product formation selectivity, with an increased voltage favoring more oxidized compounds. The glycerol concentration also affects hydrogen production, with lower concentrations yielding higher hydrogen amounts, peaking at 3.5 V for 0.05 mol L-1. This model quantitatively illustrates graphite's contribution to current and product generation in glycerol electrolyzers, emphasizing the significance of background current and products originating from current collectors if in contact with the reactants. These results have an impact on the efficiency of the electrolyzer and raise questions regarding possible extra non-noble "nonparticipating" current collectors that could affect overall performance. This research expands our understanding of electrocatalysis on graphite surfaces with potential applications in optimizing electrolyzer configurations for enhanced efficiency and product selectivity.

RESUMO

The global coconut water market is projected to grow in the upcoming years, attributed to its numerous health benefits. However, due to its susceptibility to microbial contamination and the limitations of non-thermal decontamination methods, thermal treatments remain the primary approach to ensure the shelf-life stability and the microbiological safety of the product. In this study, the thermal inactivation of Listeria innocua, a Listeria monocytogenes surrogate, was evaluated in coconut water and in tryptone soy broth (TSB) under both isothermal (50-60 °C) and dynamic conditions (from 30 to 60 °C, with temperature increases of 0.5, 1 and 5 °C/min). Mathematical models were used to analyse the inactivation data. The Geeraerd model effectively described the thermal inactivation of L. innocua in both TSB and coconut water under isothermal conditions, with close agreement between experimental data and model fits. Parameter estimates and analysis revealed that acidified TSB is a suitable surrogate medium for studying the thermal inactivation of L. innocua in coconut water, despite minor differences observed in the shoulder length of inactivation curves, likely attributed to the media composition. The models fitted to the data obtained at isothermal conditions fail to predict L. innocua responses under dynamic conditions. This is attributed to the stress acclimation phenomenon that takes place under dynamic conditions, where bacterial cells adapt to initial sub-lethal treatment stages, leading to increased thermal resistance. Fitting the Bigelow model directly to dynamic data with fixed z-values reveals a three-fold increase in D-values with lower heating rates, supporting the role of stress acclimation. The findings of this study aid in designing pasteurization treatments targeting L. innocua in coconut water and enable the establishment of safe, mild heat treatments for refrigerated, high-quality coconut water.

RESUMO

The combination of energy and chemical conversion can be achieved by designing glycerol fuel cells. However, the anode must promote the reaction at onset potentials low enough to allow a spontaneous reaction, when coupled to the cathodic reaction, and must be selective. Here, we build a three-dimensional (3D)-printed glycerol microfluidic fuel cell that produces power concomitantly to glycolate and formate at zero bias. The balance between energy and the two carbonyl compounds is tuned by decorating the Pt/C/CP anode in situ (before feeding the cell reactants) or in operando (while feeding the cell with reactants) with Bi. The Bi-modified anodes improve glycerol conversion and output power while decreasing the formation of the carbonyl compounds. The in operando method builds dendrites of rodlike Bi oxides that are inactive for the anodic reaction and cover active sites. The in situ strategy promotes homogeneous Bi decoration, decreasing activation losses, increasing the open-circuit voltage to 1.0 V, and augmenting maximum power density 6.5 times and the glycerol conversion to 72% at 25 °C while producing 0.2 mmoL L-1 of glycolate and formate (each) at 100 µL min-1. Such a performance is attributed to the low CO poisoning of the anode, which leads the glycerol electrooxidation toward a more complete reaction, harvesting more electrons at the device. Printing the microfluidic fuel cell takes 23 min and costs ∼US$1.85 and can be used for other coupled reactions since the methods of modification presented here are applied to any existing and assembled systems.

RESUMO

The objective of this study was to develop a quantitative microbial risk assessment (QMRA) model to evaluate potential risk mitigation strategies to reduce the probability of acquiring hemolytic uremic syndrome (HUS) associated with beef consumption in Argentina. Five scenarios were simulated to evaluate the effect of interventions on the probability of acquiring HUS from Shiga toxin-producing Escherichia coli (STEC)-contaminated ground beef and commercial hamburger consumption. These control strategies were chosen based on previous results of the sensitivity analysis of a baseline QMRA model. The application of improvement actions in abattoirs not applying Hazard Analysis and Critical Control Points (HACCP) for STEC would result 7.6 times lower in the probability that consumers acquired HUS from ground beef consumption, while the implementation of improvements in butcher shops would lead to a smaller reduction. In abattoirs applying HACCP for STEC, the risk of acquiring HUS from commercial hamburger consumption was significantly reduced. Treatment with 2% lactic acid, hot water and irradiation reduced 4.5, 3.5 and 93.1 times the risk of HUS, respectively. The most efficient interventions, in terms of case reduction, being those that are applied in the initial stages of the meat chain.

Assuntos

Síndrome Hemolítico-Urêmica , Escherichia coli Shiga Toxigênica , Animais , Bovinos , Síndrome Hemolítico-Urêmica/complicações , Síndrome Hemolítico-Urêmica/prevenção & controle , Ácido Láctico , Probabilidade , Água

RESUMO

Electrocatalysis is at the heart of a broad range of physicochemical applications that play an important role in the present and future of a sustainable economy. Among the myriad of different electrocatalysts used in this field, nanomaterials are of ubiquitous importance. An increased surface area/volume ratio compared to bulk makes nanoscale catalysts the preferred choice to perform electrocatalytic reactions. Bragg coherent diffraction imaging (BCDI) was introduced in 2006 and since has been applied to obtain 3D images of crystalline nanomaterials. BCDI provides information about the displacement field, which is directly related to strain. Lattice strain in the catalysts impacts their electronic configuration and, consequently, their binding energy with reaction intermediates. Even though there have been significant improvements since its birth, the fact that the experiments can only be performed at synchrotron facilities and its relatively low resolution to date (∼10 nm spatial resolution) have prevented the popularization of this technique. Herein, we will briefly describe the fundamentals of the technique, including the electrocatalysis relevant information that we can extract from it. Subsequently, we review some of the computational experiments that complement the BCDI data for enhanced information extraction and improved understanding of the underlying nanoscale electrocatalytic processes. We next highlight success stories of BCDI applied to different electrochemical systems and in heterogeneous catalysis to show how the technique can contribute to future studies in electrocatalysis. Finally, we outline current challenges in spatiotemporal resolution limits of BCDI and provide our perspectives on recent developments in synchrotron facilities as well as the role of machine learning and artificial intelligence in addressing them.

RESUMO

Calafate (Berberis microphylla G. Forst) is a wild bush plant widely distributed in the south of Argentina and Chile. Their blue colored fruits present particular flavor and health benefits attributed to high polyphenol contents biosynthesized by the plant under stress. Studies about correlation of abiotic conditions with anthocyanin profiles and physicochemical features of calafate beneath wild origin environment are not described yet. Hence, this research aimed to evaluate the physicochemical changes, antioxidant activity and anthocyanin content of calafate fruit in relationship to UV solar radiation (W.m-2) and air temperature (°C) environment condition during three consecutive years (2017, 2018, 2019). Variations in fruit anthocyanins were determined by comparison between high performance liquid chromatography (HPLC-DAD-ESI)/MSn and CIEL*a*b* colors parameters. Correlations were analyzed by principal component analysis (PCA). Radiation was negatively correlated with fruit size and weight. Physicochemical aspects such as pH, soluble solids, color, total anthocyanins, flavanols and other phenolic compounds were positively correlated with temperature changes. The quantities of monomeric anthocyanins were dependent on both low temperature and global radiation (reaching 20.01 mg g-1 FW in calafate fruit). These results constitute a valuable resource to understand the structural and physiological plasticity of calafate in facing climate changes for future domestication research as well as for agri-food industrial application.

RESUMO

We developed a quantitative microbiological risk assessment (QMRA) of haemolytic uremic syndrome (HUS) associated with Shiga toxin-producing Escherichia coli (STEC)-contaminated beef (intact beef cuts, ground beef and commercial hamburgers) in children under 15 years of age from Argentina. The QMRA was used to characterize STEC prevalence and concentration levels in each product through the Argentinean beef supply chain, including cattle primary production, cattle transport, processing and storage in the abattoir, retail and home preparation, and consumption. Median HUS probability from beef cut, ground beef and commercial hamburger consumption was <10-15, 5.4x10-8 and 3.5x10-8, respectively. The expected average annual number of HUS cases was 0, 28 and 4, respectively. Risk of infection and HUS probability were sensitive to the type of abattoir, the application or not of Hazard Analysis and Critical Control Points (HACCP) for STEC (HACCP-STEC), stx prevalence in carcasses and trimmings, storage conditions from the abattoir to retailers and home, the joint consumption of salads and beef products, and cooking preference. The QMRA results showed that the probability of HUS was higher if beef cuts (1.7x) and ground beef (1.2x) were from carcasses provided by abattoirs not applying HACCP-STEC. Thus, the use of a single sanitary standard that included the application of HACCP-STEC in all Argentinean abattoirs would greatly reduce HUS incidence. The average number of annual HUS cases estimated by the QMRA (n = 32) would explain about 10.0% of cases in children under 15 years per year in Argentina. Since other routes of contamination can be involved, including those not related to food, further research on the beef production chain, other food chains, person-to-person transmission and outbreak studies should be conducted to reduce the impact of HUS on the child population of Argentina.

Assuntos

Síndrome Hemolítico-Urêmica/microbiologia , Carne Vermelha/microbiologia , Adulto , Animais , Argentina , Bovinos , Criança , Dieta , Escherichia coli/fisiologia , Feminino , Contaminação de Alimentos , Armazenamento de Alimentos , Humanos , Masculino , Medição de Risco

RESUMO

The glycerol electrooxidation reaction (GEOR) has attracted huge interest in the last decade due to the very low price and availability of this polyol. In this work, we studied the GEOR on Pt(111) electrodes by introducing different densities of random defects. Our results showed that the generation of defects on Pt(111) slightly modified the GEOR onset potential, however it generates changes in the voltammetric oxidation charges and also in the relative production of CO2 to carbonyl containing compounds, C[double bond, length as m-dash]O. The voltammetric profiles in the forward scan show two oxidation peaks. FTIR data show that the first one is connected with the GlOH dissociative adsorption to form CO (and others intermediates) while the second one, at higher potentials, matches the onsets of the CO oxidation to CO2 and the C[double bond, length as m-dash]O production. FTIR also confirms that the lower activity of defected electrodes at lower potentials is connected to a higher CO poisoning. DFT calculations show that the presence of CO molecules on a Pt defected surface keeps water and GlOH molecules far from the surface and linked by H bonds. This paper is the last of a series of three works where we explore the GEOR on an important number of different Pt surfaces. These works show that it is difficult to oxidize GlOH at potentials lower than 0.6 V (under our experimental conditions) without suffering an important electrode poisoning (mainly by CO). Since the structure of nanoparticles might be mimicked by defected single crystals, these sets of reports provide a considerable amount of information concerning the influence of such surfaces towards GlOH reaction in acidic media. Therefore, if the well-known "nano"-effect does not produce substantial changes in the activity of Pt materials, they are not useful to be applied in a Direct Glycerol Fuel Cell (DGFC). On the other hand, it is very interesting that the density of electrode defects permits us to tune the relative production of CO2 to C[double bond, length as m-dash]O.