Role of Clay Substrate Molecular Interactions in Some Dairy Technology Applications.

The use of clay materials in dairy technology requires a multidisciplinary approach that allows correlating clay efficiency in the targeted application to its interactions with milk components. For profitability reasons, natural clays and clay minerals can be used as low-cost and harmless food-compatible materials for improving key processes such as fermentation and coagulation. Under chemical stability conditions, clay materials can act as adsorbents, since anionic clay minerals such as hydrotalcite already showed effectiveness in the continuous removal of lactic acid via in situ anion exchange during fermentation and ex situ regeneration by ozone. Raw and modified bentonites and smectites have also been used as adsorbents in aflatoxin retention and as acidic species in milk acidification and coagulation. Aflatoxins and organophilic milk components, particularly non-charged caseins around their isoelectric points, are expected to display high affinity towards high silica regions on the clay surface. Here, clay interactions with milk components are key factors that govern adsorption and surface physicochemical processes. Knowledge about these interactions and changes in clay behavior according to the pH and chemical composition of the liquid media and, more importantly, clay chemical stability is an essential requirement for understanding process improvements in dairy technology, both upstream and downstream of milk production. The present paper provides a comprehensive review with deep analysis and synthesis of the main findings of studies in this area. This may be greatly useful for mastering milk processing efficiency and envisaging new prospects in dairy technology.

Role of Silica on Clay-Catalyzed Ozonation for Total Mineralization of Bisphenol-A.

Catalytic ozonation for the total mineralization of bisphenol-A (BPA) from aqueous solution was investigated in the presence of various silica-based catalysts such as mesoporous silica, acid-activated bentonite (HMt) and montmorillonite-rich materials (Mt) ion-exchanged with Na+ and Fe2+ cations (NaMt and Fe(II)Mt). The effects of the catalyst surface were studied by correlating the hydrophilic character and catalyst dispersion in the aqueous media to the silica content and BPA conversion. To the best of our knowledge, this approach has barely been tackled so far. Acid-activated and iron-free clay catalysts produced complete BPA degradation in short ozonation times. The catalytic activity was found to strongly depend on the hydrophilic character, which, in turn, depends on the Si content. Catalyst interactions with water and BPA appear to promote hydrophobic adsorption in high Si catalysts. These findings are of great importance because they allow tailoring silica-containing catalyst properties for specific features of the waters to be treated.

Clay-Catalyzed Ozonation of Hydrotalcite-Extracted Lactic Acid Potential Application for Preventing Milk Fermentation Inhibition.

An unprecedented route for mitigating the inhibitory effect of lactic acid (LA) on milk fermentation was achieved through lactate adsorption on hydrotalcite (Ht) from simulated lactate extracts. During its regeneration by ozonation, Ht displayed catalytic activity that appeared to increase by addition of montmorillonite (Mt). Changes in the pH, Zeta potential and catalyst particle size during LA ozonation were found to strongly influence LA-LA, LA-catalyst and catalyst-catalyst interactions. The latter determine lactate protonation-deprotonation and clay dispersion in aqueous media. The activity of Mt appears to involve hydrophobic adsorption of non-dissociated LA molecules on silica-rich areas at low pH, and Lewis acid-base and electrostatic interactions at higher pH than the pKa. Hydrotalcite promotes both hydrophobic interaction and anion exchange. Hydrotalcite-smectite mixture was found to enhance clay dispersion and catalytic activity. This research allowed demonstrating that natural clay minerals can act both as adsorbents for LA extract from fermentation broths and as catalysts for adsorbent regeneration. The results obtained herein provide valuable and useful findings for envisaging seed-free milk clotting in dairy technologies.

Clay-catalyzed ozonation of endocrine-disrupting compounds in solvent-free media - to better understand soil catalytic capacity.

An original approach never tackled so far allowed correlating the basicity and hydrophilic character of clay catalysts to surface interaction with 17α-Ethinylestradiol (EE2) during ozonation in water. The clay catalysts were found to behave specifically according to their silica/alumina ratio like soils in natural oxidative processes. Acid-activated bentonites (HMt) and ion-exchanged montmorillonite (NaMt and Fe(ii)Mt) showed catalytic activity in the ozonation of 17α-ethinylestradiol (EE2) in aqueous media. In the absence of catalysts, the degradation of (EE2) reached 72% after one minute of ozonation and 99.5% after 60 minutes. In the presence of Fe(ii)Mt, EE2 degradation (96%) was achieved after only one minute of ozonation. Under similar conditions, almost total degradation to 99.99% was registered in 15 minutes of ozonation but without total mineralization of the intermediates. Moderately acid-activated bentonites exhibited higher activity affording total mineralization within a short period of ozonation. The catalytic activity of clay catalysts was found to correlate with their surface basicity and hydrophilic character. The results obtained herein allow understanding soil behavior in natural oxidative degradation of organic molecules and envisaging effective soil-based catalysts with surface properties judiciously tailored according to the nature of organic pollutants in solvent free media.

Acid-treated clay catalysts for organic dye ozonation - Thorough mineralization through optimum catalyst basicity and hydrophilic character.

Catalytic ozonation of Methylene Blue, Methyl Green, Methyl Orange and Methyl-thymol Blue was investigated in the presence of ion-exchanged montmorillonite (NaMt and Fe(II)Mt), crude bentonite and acid-activated counterparts. An original approach never tackled so far consisted in correlating the basicity and hydrophilic character to the dye-catalyst interactions occurring on the catalyst surface. This was achieved through CO2 and water thermal programmed desorption. Kinetics study revealed that ozonation starts in the bulk solution, and dye adsorption turns out to be an essential requirement for high catalytic effectiveness. On NaMt, dye molecules appear to adsorb mainly via hydrophobic interaction. On Fe(II)Mt, the contributions of hydrophobic interaction, cation-exchange and Fe2+ mobility to the catalytic activity prevail. Acid activated clay catalysts exhibited lowest hydrophilic character favoring adsorption through organophilic interaction and affording thorough and fast dye mineralization. This was explained in terms of increased number of silanols and -Si-O-Si- groups. For all catalysts, short ozonation of all dye molecules resulted in similar end-chain products, which were totally eliminated after prolonged reaction times. This result is of great importance because it provides valuable theoretical findings that allow envisaging total mineralization of organic molecules by recyclable metal-free clay catalysts.

Cu0-Loaded organo-montmorillonite with improved affinity towards hydrogen: an insight into matrix-metal and non-contact hydrogen-metal interactions.

Copper-loaded organo-montmorillonite showed improved affinity towards hydrogen under ambient conditions. Clay ion exchange with a propargyl-ended cation followed by thiol-yne coupling with thioglycerol resulted in a porous structure with a 6 fold higher specific surface area, which dramatically decreased after copper incorporation. X-ray diffraction and photoelectron spectrometry, nuclear magnetic resonance (1H and 13C) and CO2-thermal programmed desorption revealed strong sulfur:Cu0 and oxygen:Cu0 interactions. This was explained in terms of structure compaction that 'traps' Cu0 nanoparticles (CuNPs) and reduces their mobility. Transmission electron microscopy showed predominant 1.0-1.5 nm CuNPs. Hydrogen capture appears to involve predominantly physical interaction, since differential scanning calorimetry measurements gave low desorption heat and almost complete gas release between 20 °C and 75 °C. Possible hydrogen condensation within the compacted structure should hinder gas diffusion inside CuNPs and prevent chemisorption. These results allow safe hydrogen storage with easy gas release to be envisaged even at room temperature under vacuum. The reversible capture of hydrogen can be even more attractive when using natural inorganic supports and commercial plant-derived dendrimers judiciously functionalized, even at the expense of porosity.

Modelling of Batch Lactic Acid Fermentation inthe Presence of Anionic Clay.

Batch fermentation of milk inoculated with lactic acid bacteria was conducted in the presence of hydrotalcite-type anionic clay under static and ultrasonic conditions. An experimental study of the effect of fermentation temperature (t=38-43 °C), clay/milk ratio (R=1-7.5 g/L) and ultrasonic field (ν=0 and 35 kHz) on process dynamics was performed. A mathematical model was selected to describe the fermentation process kinetics and its parameters were estimated based on experimental data. A good agreement between the experimental and simulated results was achieved. Consequently, the model can be employed to predict the dynamics of batch lactic acid fermentation with values of process variables in the studied ranges. A statistical analysis of the data based on a 23 factorial experiment was performed in order to express experimental and model-regressed process responses depending on t, R and ν factors.