Neutral pH Research Articles

Biogenic Synthesis Based on Cuprous Oxide Nanoparticles Using Eucalyptus globulus Extracts and Its Effectiveness for Removal of Recalcitrant Compounds

Recalcitrant compounds resulting from anthropogenic activity are a significant environmental challenge, necessitating the development of advanced oxidation processes (AOPs) for effective remediation. This study explores the synthesis of cuprous oxide nanoparticles on cellulose-based paper (Cu2O@CBP) using Eucalyptus globulus leaf extracts, leveraging green synthesis techniques. The scanning electron microscopy (SEM) analysis found the average particle size 64.90 ± 16.76 nm, X-ray diffraction (XRD) and Raman spectroscopy confirm the Cu2O structure in nanoparticles; Fourier-transform infrared spectroscopy (FTIR) suggests the reducing role of phenolic compounds; and ultraviolet–visible diffuse reflectance spectroscopy (UV-Vis DRS) allowed us to determine the band gap (2.73 eV), the energies of the valence band (2.19 eV), and the conduction band (−0.54 eV) of Cu2O@CBP. The synthesized Cu2O catalysts demonstrated efficient degradation of methylene blue (MB) used as a model as recalcitrant compounds under LED-driven visible light photocatalysis and heterogeneous Fenton-like reactions with hydrogen peroxide (H2O2) using the degradation percentage and the first-order apparent degradation rate constant (kapp). The degradation efficiency of MB was pH-dependent, with neutral pH favoring photocatalysis (kapp = 0.00718 min−1) due to enhanced hydroxyl (·OH) and superoxide radical (O2·−) production, while acidic pH conditions improved Fenton-like reaction efficiency (kapp = 0.00812 min−1) via ·OH. The reusability of the photocatalysts was also evaluated, showing a decline in performance for Fenton-like reactions at acidic pH about 22.76% after five cycles, while for photocatalysis at neutral pH decline about 11.44% after five cycles. This research provides valuable insights into the catalytic mechanisms and supports the potential of eco-friendly Cu2O nanoparticles for sustainable wastewater treatment applications.

Development of cyclodextrin-electrokinetic chromatography-based strategies for the separation of ketorolac enantiomers

The development of analytical strategies enabling the chiral separation of ketorolac by electrokinetic chromatography is presented in this work. This anti-inflammatory drug is commercialised as racemic mixture but its physiological activity resides in the S-enantiomer. Different experimental conditions were investigated at acidic and neutral pH, including the use of cyclodextrins (CD) or amino acid-based ionic liquids (AAILs) ([TMA][L-Cit], [TMA][L-Arg], [TMA][L-Harg], [TBA][L-Cit], [TBA][L-Arg], and [TBA][L-Harg]) as the sole chiral selectors or the combination of a CD with AAILs or their cationic components (tetramethylammonium (TMA-OH) or tetrabutylammonium (TBA-OH)). The best conditions in terms of migration times and enantiomeric resolutions were obtained using 2 mM heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD) in 50 mM phosphate buffer at pH 7.0 or 2 mM TM-β-CD with 60 mM TMA-OH in 50 mM formate buffer at pH 3.0. The presence of TMA-OH in the separation medium affected considerably the electroosmotic flow (EOF) mobility which, in turn, significantly shortened the migration times for ketorolac enantiomers at pH 3.0 due to an inversion in the EOF. The multivariate optimization of the experimental conditions for the single system and for the combined system with TMA-OH enabled to obtain the separation of ketorolac enantiomers in less than 11 min with enantiomeric resolutions of 2.5 and 1.9, respectively. The single system was selected to evaluate its analytical characteristics in terms of limits of detection/quantification, accuracy, and precision, according to the International Council for Harmonization (ICH) guidelines, which resulted adequate to be applied to the analysis of pharmaceutical formulations.

Catalytic Nanomaterials by Conjugation of an Artificial Heme-Peroxidase to Amyloid Fibrils.

The self-assembly of proteins and peptides into fibrillar amyloid aggregates is a highly promising route to define the next generation of functional nanomaterials. Amyloid fibrils, traditionally associated with neurodegenerative diseases, offer exceptional conformational and chemical stability and mechanical properties, and resistance to degradation. Here, we report the development of catalytic amyloid nanomaterials through the conjugation of a miniaturized artificial peroxidase (FeMC6*a) to a self-assembling amyloidogenic peptide derived from human transthyretin, TTR(105-115), whose sequence is YTIAALLSPYS. Our synthetic approach relies on fast and selective click ligation upon proper modification of both the peptide and FeMC6*a, leading to TTRLys108@FeMC6*a. Mixing unmodified TTR(105-115) with TTRLys108@FeMC6*a allowed the generation of enzyme-loaded amyloid fibrils, namely, FeMC6*a@fibrils. Catalytic studies, performed in aqueous solution at nearly neutral pH, using ABTS as a model substrate and H2O2 as the oxidizing agent revealed that the enzyme retains its catalytic activity. Moreover, the activity was found to depend on the TTRLys108@FeMC6*a/unmodified TTR(105-115) peptide ratio. In particular, those with the 2:100 ratio showed the highest activity in terms of initial rates and substrate conversion among the screened nanoconjugates and compared to the freely diffusing enzyme. Finally, the newly developed nanomaterials were integrated into a flow system based on a polyvinylidene difluoride membrane filter. Within this flow-reactor, multiple reaction cycles were performed, showcasing the reusability and stability of the catalytic amyloids over extended periods, thus offering significantly improved characteristics compared to the isolated FeMC6*a in the application to a number of practical scenarios.

Proton-triggered rearrangement of the AMPA receptor N-terminal domains impacts receptor kinetics and synaptic localization.

AMPA glutamate receptors (AMPARs) are ion channel tetramers that mediate the majority of fast excitatory synaptic transmission. They are composed of four subunits (GluA1-GluA4); the GluA2 subunit dominates AMPAR function throughout the forebrain. Its extracellular N-terminal domain (NTD) determines receptor localization at the synapse, ensuring reliable synaptic transmission and plasticity. This synaptic anchoring function requires a compact NTD tier, stabilized by a GluA2-specific NTD interface. Here we show that low pH conditions, which accompany synaptic activity, rupture this interface. All-atom molecular dynamics simulations reveal that protonation of an interfacial histidine residue (H208) centrally contributes to NTD rearrangement. Moreover, in stark contrast to their canonical compact arrangement at neutral pH, GluA2 cryo-electron microscopy structures exhibit a wide spectrum of NTD conformations under acidic conditions. We show that the consequences of this pH-dependent conformational control are twofold: rupture of the NTD tier slows recovery from desensitized states and increases receptor mobility at mouse hippocampal synapses. Therefore, a proton-triggered NTD switch will shape both AMPAR location and kinetics, thereby impacting synaptic signal transmission.

Colorimetric and fluorescent dual-mode detection of Escherichia coli using Fe3O4 nanoparticle coated with fluorescein-labeled aptamer

Ensuring the reliable and accurate detection of Escherichia coli (E. coli) is essential for maintaining food safety and safeguarding human health. In this work, a dual-mode sensor that integrates colorimetric and fluorescence detection was developed for the precise identification of E. coli. Fe3O4 nanoparticles (NPs) were coated with a fluorescein-labeled aptamer (FAM-Apt) to enhance their peroxidase-like activity under neutral pH conditions. Simultaneously, this coating also effectively suppressed the fluorescence emitted by FAM. Upon exposure to E. coli, specific binding of the bacteria causes the detachment of FAM-Apt from the Fe3O4 NPs surface, resulting in the suppression of Fe3O4 NPs catalytic activity under neutral pH and the alleviation of the quenching effect on FAM fluorescence. This leads to a simultaneous decrease in the colorimetric signal and an increase in fluorescence signal, facilitating the development of a dual-mode detection method for E. coli with an impressive limit of detection (LOD) of 10 CFU/mL in the colorimetric mode and 6 CFU/mL in the fluorescence mode. This approach highlights the untapped potential of Fe3O4 NPs as a peroxidase mimic in dual-mode sensors, offering a promising strategy for E. coli detection with significant implications for enhancing food safety and public health practices.

Activity of botulinum neurotoxin X and its structure when shielded by a non-toxic non-hemagglutinin protein

Botulinum neurotoxins (BoNTs) are the most potent toxins known and are used to treat an increasing number of medical disorders. All BoNTs are naturally co-expressed with a protective partner protein (NTNH) with which they form a 300 kDa complex, to resist acidic and proteolytic attack from the digestive tract. We have previously identified a new botulinum neurotoxin serotype, BoNT/X, that has unique and therapeutically attractive properties. We present the cryo-EM structure of the BoNT/X-NTNH/X complex and the crystal structure of the isolated NTNH protein. Unexpectedly, the BoNT/X complex is stable and protease-resistant at both neutral and acidic pH and disassembles only in alkaline conditions. Using the stabilizing effect of NTNH, we isolated BoNT/X and showed that it has very low potency both in vitro and in vivo. Given the high catalytic activity and translocation efficacy of BoNT/X, low activity of the full toxin is likely due to the receptor-binding domain, which presents very weak ganglioside binding and exposed hydrophobic surfaces.

PH Dependence of Noble Metals Dissolution: Gold

AbstractThe electrochemical applications of gold span the entire pH spectrum. Recently, gold dissolution in acidic and alkaline media has been studied, but less attention has been given to electrolytes at intermediate pH values. To address this gap, this work uses on‐line electrochemical dissolution inductively coupled plasma mass spectrometry (ICP‐MS) to examine gold dissolution across a pH range of 1 to 12.7 using phosphate buffer solutions. All experimental parameters, except pH, are kept constant, enabling a clear investigation of pH effects on anodic (gold oxidation) and cathodic (gold oxide reduction) dissolution processes. Results show that dissolution amounts are lowest at neutral pH values between 3 and 7, varying with the applied potential and exposure time. Anodic and cathodic dissolution dominate in acidic and alkaline electrolytes, respectively. Depending on the highest applied potentials and time exposure, the main dissolution mechanism shifts at pH=5, 7, and 9. The pH dependence of Au dissolution is proposed to be linked to the nature of gold oxides formed, the kinetics of oxide formation/reduction, gold ion redeposition, and the influence of the oxygen evolution reaction (OER) on dissolution. These results provide fundamental insights into gold dissolution under neutral pH conditions.

Predictive Functional Profiling Reveals Putative Metabolic Capacities of Bacterial Communities in Drinking Water Resources and Distribution Supply in Mega Manila, Philippines

Assessing bacterial communities across water resources is crucial for understanding ecological dynamics and improving water quality management. This study examines the functional profiles of bacterial communities in drinking water resources in Mega Manila, Philippines, including Laguna Lake tributaries, pre-treatment plant sites, groundwater sources, and post-treatment plant sites. Using eDNA sequencing, flux balance analysis, and taxonomy-to-phenotype mapping, we identified metabolic pathways involved in nutrient metabolism, pollutant degradation, antibio- tic synthesis, and nutrient cycling. Despite site variations, there are shared metabolic pathways, suggesting the influence of common ecological factors. Site-specific differences in pathways like ascorbate, aldarate, and phenylalanine metabolism indicate localized environmental adaptations. Antibiotic synthesis pathways, such as streptomycin and polyketide sugar unit biosynthesis, were detected across sites. Bacterial communities in raw and pre-treatment water showed potential for pollutant degradation such as for endocrine-disrupting chemicals. High levels of ammonia-oxidizing and sulfate-reducing bacteria in pre- and post-treatment water suggest active nitrogen removal and pH neutralization, indicating a need to reassess existing water treatment approaches. This study underscores the adaptability of bacterial communities to environmental factors, as well as the importance of considering their functional profiles in assessing drinking water quality resources in urban areas.

Efficacy of nitrogen and Azolla spp. on growth and yield of black rice (Oryza sativa L.)

An experimental field study was carried out in the Kharif season of 2023 at the Crop Research Farm, Department of Agronomy, SHUATS, Prayagraj (U.P.). The experimental replications were conducted using a Randomized Block Design, with three levels of Nitrogen (0, 60, 90kg N/ha) and Azolla spp. (2, 4, 6t/ha), and one Control (NPK 120:60:60 kg/ha). In all, there were a total of ten treatments, each reproduced three times. The tested field had sandy loam soil texture with a neutral soil pH of 7.6, low organic carbon content of 0.372%, nitrogen content of 278.4 kg/ha, phosphorous content of 29.5 kg/ha, and potassium level of 217.3 kg/ha. The experimental results showed that treatment T₉ obtained significantly higher plant height (107.77 cm), dry weight (66.05 g), crop growth rate (57.27 g/m2/day), relative growth rate (0.0279 g/g/day), highest number of tillers per hill (22.07), panicles per m2 (282), test weight (15.23 g), grain yield (3.67 t/ha), stover yield (6.7 t/ha), and harvest index (35.74%). Transplanted Black Rice of variety BPT-2841 exhibited significantly greater maximum gross return (1,80,551.40 INR/ha), net return (1,05,496.30 INR/ha), and B:C ratio (1.41) in treatment T9. The investigation concludes that Nitrogen, being easily transportable in soil and plants, is a constituent of amino acids, nucleic acids, chlorophyll, enzymes, and hormones. These factors are essential in plant physiology and are associated with increased tillering, biomass production, protein synthesis, grain filling, yield, and quality. The availability, absorption, and utilization of nitrogen have a significant impact on these processes. Therefore, in the present experiment, the nitrogen requirements are met by applying 90kg of nitrogen through urea combined with 6t/ha of Azolla spp. This approach revealed superior performance in terms of both crop yield and economic returns .

Differences in growth and survival of two varieties of Ochroma pyramidale in rustic plantations in southern Mexico

Ochroma pyramidale (Cav. Ex Lam.) is a rapidly growing pioneer tree native to the Americas. This species is important for rehabilitating degraded areas as well as commercially due to the wood`s low density and high resistance, making it useful for producing structural cores and lightweight plywood, as well as in the wind energy industry. For at least 50 years, two varieties of this species have been recognized by botanists as well as the Lacandon people of Chiapas, Mexico. This study provides comparative data regarding three years of growth of the white and red varieties of Ochroma pyramidale, indicating ideal soil and climatic conditions for commercial plantations. The white variety had a greater rate of growth and thrives with a high average annual precipitation (2330–3236 mm) and Luvisol or Leptosol with a neutral pH and a high P content. The red variety appears to be the most widely used in other regions of the world, while the white variety is rarely used commercially.

Physicochemical characterization of novel okra mucilage/hyaluronic acid-based oral disintegrating films for functional food applications

Oral disintegrating films (ODFs) offer a patient-friendly approach with enhanced convenience and rapid onset of action over various health benefits. ODFs are fabricated for geriatric, pediatric, and individuals facing swallowing challenges. The present work aims to fabricate and characterize ODFs mainly composed of okra mucilage (OM), hyaluronic acid (HA), vitamin-C-loaded bioactive glass nanoparticles (VBG NPs), and clove essential oil. A bio-inspired method was employed to synthesize VBG NPs using fructose template. The nutrient analysis of OM depicted that it is a rich source of protein, carbohydrates, magnesium, and flavonoids (quercetin), accounting for its antioxidant activity. The physicochemical characteristics of the ODFs studied using contact angle measurement, surface pH, opacity, and in vitro disintegration time revealed that ODFs disintegrated rapidly in simulated saliva. The neutral surface pH of ODFs indicates their non-irritant behaviour to the oral mucosa. VBG NPs and essential oil (EO) addition enhance the thermal and mechanical properties. Further, EO infusion in the film matrix resulted in the porous and antibacterial nature of the functional film as revealed by FE-SEM micrographs and antibacterial disk diffusion assay respectively. The obtained novel nutrient-rich ODF is hemocompatible with a hemolysis rate (HR%) <5 % and suitable for functional food applications.

Galectin-2 Agglutinates Helicobacter pylori via Lipopolysaccharide Containing H Type I Under Weakly Acidic Conditions.

Galectins are β-galactoside-binding animal lectins involved in various biological functions, such as host defense. Galectin-2 and -3 are members of the galectin family that are expressed in the stomach, including the gastric mucosa and surface mucous cells. Galectin-3 exhibits aggregation and bactericidal activity against Helicobacter pylori in a β-galactoside-dependent manner. We previously reported that galectin-2 has the same activity under neutral pH conditions. In this study, the H. pylori aggregation activity of galectin-2 was examined under weakly acidic conditions, in which H. pylori survived. Galectin-2 agglutinated H. pylori even at pH 6.0, but not at pH 5.0, correlating with its structural stability, as determined using circular dichroism. Additionally, galectin-2 binding to the lipopolysaccharide (LPS) of H. pylori cultured under weakly acidic conditions was investigated using affinity chromatography and Western blotting. Galectin-2 could bind to H. pylori LPS containing H type I, a Lewis antigen, in a β-galactoside-dependent manner. In contrast, galectin-3 was structurally more stable than galectin-2 under acidic conditions and bound to H. pylori LPS containing H type I and Lewis X. In conclusion, galectin-2 and -3 might function cooperatively in the defense against H. pylori in the stomach under different pH conditions.

(Invited) On Solar Seawater Splitting

We are currently witnessing the widest worldwide environmental disasters and it is now crucial for the future of humanity to transition to novel societies where environmental, energy, and economic policies are no longer based on endless-growth financial models and fossil fuel technologies to decrease our environmental footprint. The origin of this strong imbalance between human activities and the environment is found in the endless-growth economic systems in place in major countries worldwide as it inherently requires the use of endless cheap energy to be sustained, hence the massive use of coal and fossil fuels as energy sources for a more profitable energy return on energy invested, which might be good for the economy but not for our environment, health, and sustainable future. Technological innovations have always helped boost the economy numerous times throughout civilizations yet it must involve large-scale, clean, and cost-effective fabrication techniques and be based on efficient earth-abundant and easily recyclable materials. A transition to hydrogen-based energy and economy is ideal as it produces zero carbon emission and hydrogen fuel cell and forthcoming hydrogen combustion transportation are available worldwide. However, most of the hydrogen produced comes from nonrenewable sources, i.e. by steam reforming of methane which produces very large amount of carbon mono/dioxide. The most natural, cleanest and sustainable way to produce hydrogen at large scale is by solar seawater splitting[1]. Our strategy is to fabricate earth-abundant and non-toxic devices consisting of oriented arrays of quantum rods/dots of high purity synthesized by aqueous chemical growth at low temperature without surfactant and with controlled dimensionalities and surface chemistry[2] with intermediate bands for high visible-light conversion, band structure edges optimized for stability against photocorrosion and operation conditions at neutral pH, low bias and no sacrificial agent. Such characteristics, combined with the in-depth investigation of their size dependent and interfacial electronic structure[3] and electrical properties[4] provide better fundamental understanding and structure-efficiency relationships for a cost-effective and sustainable generation of hydrogen from the two most abundant and geographically-balanced free resources available, the sun and seawater. An overview of such a strategy is presented for oxides, nitrides, sulfides as well as semiconductor-molecular catalysts hybrids[5], their low-cost and large scale fabrication, physical characterization, photogenerated charge dynamics, dopant segregation and thermal processing effects[1].[1] K.C. Bedin et al J. Am. Ceram. Soc. 2023, 106, 79; I. Rodriguez-Gutierrez et al ECS J. Solid State Sci. Tech. 2022, 11, 043001; J. B. Souza Jr et al Appl. Phys. Lett. 2021, 119, 200501; Y. Chen et al J. Mater. Chem. C 2021, 9, 3726; A. Tofanello et al J. Appl. Phys. 2020, 128, 063103; APL Mater. 2020, 8, 040905; Y. Wei et al Sol. Energy Mater. Sol. Cells 2019, 201, 110083; X. Guan et al ACS Energy Lett. 2018, 3, 2230; J. Phys. Chem. C 2018, 122, 13797; J. Su et al J. Phys. Chem. Lett. 2017, 8, 5228; ACS Energy Lett. 2016, 1, 121; Y. Tachibana et al Nat. Photon. 2012, 6, 511; C.X. Kronawitter et al Energy Environ. Sci. 2011, 4, 3889[2] L.Vayssieres, Adv. Mater. 2003, 15, 464; Int. J. Nanotechnol. 2004 , 1, 1; Int. J. Nanotechnol. 2005, 2, 411; J. Phys. Chem. C 2009, 113, 4733; J. Lützenkirchen et al Colloids Interfaces 2020, 4, 39[3] L.Vayssieres et al Appl. Phys. Lett. 2011 99, 183101; Adv. Mater., 2005, 17, 2320; C.X. Kronawitter et al Phys. Rev. B 2012, 85, 125109; Energy Environ. Sci. 2014, 7, 3100; Nano Lett. 2011, 11, 3855; J. Phys. Chem. C 2012, 116, 22780; PhysChemChemPhys 2013, 15, 13483; M.G. Kibria et al Adv. Mater. 2016, 28, 8388; K. Nie et al Nano Energy 2018, 53, 493; C.L. Dong et al Chem. Eur. J. 2018, 24, 18356[4] J. Wang et al ACS Appl. Mater. Interfaces 2019, 11, 2031; J. Engel et al Adv. Func. Mater. 2014, 24, 4952; I. Rodriguez-Gutierrez et al Electrochim. Acta 2019, 308, 317; Appl. Phys. Lett. 2021, 119, 071602; K. C. Bedin et al Chin. J. Catal. 2022, 43, 1247[5] T. Benko et al Catal. Sci. Technol. 2021, 11, 6411; Y. Wei et al Nano Res. 2016, 9, 156

Solar Flow Battery for Grid Innovation: Exploring Novel Cell Designs and Osmotically Balanced Neutral pH Electrolytes

The demand for clean and efficient energy with low carbon emissions has been increased continuously. In 2022, 29.9% of global electricity production came from renewable energy sources, and the UK contributed a relatively high percentage of 41.5%. However, it appears to lag behind the Nordic countries, showing an impressive 81.2% of its electricity from renewable sources. The primary hurdle to expanding the share of renewable energy is intermittency. There is a crucial need for research and development in energy storage systems to enhance this aspect. Among various renewable energy storage technologies, redox flow battery (RFB) has recently come into the spotlight because of its scalability, long-term storage capability, and fast kinetics. However, the highly concentrated acidic condition and high voltage of the conventional RFB electrolytes make applying this technology for the integration of Photovoltaic cells difficult. Here, we report a, efficient solar-rechargeable redox flow battery (SRFB) with significantly enhanced safety and stability. Particularly, we introduce a competitive osmotically-balanced neutral pH aqueous Iodine/Bromine electrolyte combination, which has not been used for solar-to-electricity storage technologies. The present work holds great potential for safe and reliable charging/discharging operations to existing photovoltaic-assisted battery technologies. These results promote the utilization of existing solar cell facilities and are a cornerstone for the development of SFBs for practical and efficient energy storage devices.

Influence of pH on the emulsifying property of high methyl-esterified citrus pectin in the presence of calcium cations

High methyl-esterified citrus pectin (HMCP) is often used as a thickness in food products and is considered a poor emulsifier, especially in neutral pH solutions. Our previous findings show that the emulsifying capacity of HMCP could be significantly enhanced by calcium cations. Besides, the pH of the solution decreased in the presence of calcium cations. However, the impact of solution pH on HMCP emulsifying capacity in the presence of calcium cations is unclear. In this study, the pH of the HMCP solution was adjusted from 3.00 to 8.00 before adding calcium cations. The solution properties and emulsifying properties were analyzed in light of the existence of calcium cations. The results showed that the pH of the HMCP solutions decreased after bringing calcium cations into them. Calcium cations could change the solution rheological properties, particle size distributions and morphologies, and the particle microenvironmental hydrophobic areas in HMCP solutions while increasing the pH of HMCP solutions, contributing to improving the emulsifying capacity of HMCP. HMCP had the best emulsifying ability when the pH of the HMCP solutions was kept at a neutral level. This research gives us new ideas to adjust the emulsifying property of HMCP.

Aspergillus niger Ochratoxinase Is a Highly Specific, Metal-Dependent Amidohydrolase Suitable for OTA Biodetoxification in Food and Feed.

Microbial enzymes can be used as processing aids or additives in food and feed industries. Enzymatic detoxification of ochratoxin A (OTA) is a promising method to reduce OTA content. Here, we characterize the full-length enzyme ochratoxinase (AnOTA), an amidohydrolase from Aspergillus niger. AnOTA hydrolyzes OTA and ochratoxin B (OTB) mycotoxins efficiently and also other substrates containing phenylalanine, alanine, or leucine residues at their C-terminal position, revealing a narrow specificity profile. AnOTA lacks endopeptidase or aminoacylase activities. The structural basis of the molecular recognition by AnOTA of OTA, OTB, and a wide array of model substrates has been investigated by molecular docking simulation. AnOTA shows maximal hydrolytic activity at neutral pH and high temperature (65 °C) and retained high activity after prolonged incubation at 45 °C. The reduction of OTA levels in food products by AnOTA has been investigated using several commercial plant-based beverages. The results showed complete degradation of OTA with no detectable modification of beverage proteins. Therefore, the addition of AnOTA seems to be a useful procedure to eliminate OTA in plant-based beverages. Moreover, computational predictions of in vivo characteristics indicated that AnOTA is neither an allergenic nor antigenic protein. All characteristics found for AnOTA supported the suitability of its use for OTA detoxification in food and feed.

Carbon dioxide emissions from temperate reservoirs and pit lakes of different trophic states

The abundance of human-made inland waters, such as artificial ponds and reservoirs, has multiplied over the last decades. Compared to natural lakes, reservoirs and retention basins can exhibit a higher accumulation of organic carbon and a higher emission of greenhouse gases. Magnitude and dynamics of related emission fluxes are important to understand the role of inland waters in the global carbon cycle. However, origin and use of artificial waterbodies are diverse, and it is unclear whether current gas flux estimates adequately represent all important types and conditions of artificial inland waters. This study compares drivers of CO2 and CH4 emissions from two types of temperate artificial waters that are widespread in central Europe: reservoirs and artificial lakes in former open-pit lignite mines (pit lakes). We measured CO2 exchange at the water surface, calculated surface water CO2 from long-term DIC and pH data, and measured CO2 and CH4 concentrations throughout the water column. We found that an older, eutrophic pit lake showed seasonal variations in CO2 fluxes including uptake during summer and release during turnover, similar to three studied freshwater reservoirs. In contrast, reacidification and repeated addition of carbonate (liming) led to sustained CO2 supersaturation in a young, oligotrophic pit lake throughout the year, potentially making it a steady source of CO2 to the atmosphere. This implies that on an annual level, pH regulation and lake maturity largely determine whether pit lakes act as sources of CO2 (young, slightly acidic) or sinks of CO2 (older, neutral pH).

Proton Transfer Kinetics in Histidine Side Chains Determined by pH-Dependent Multi-Nuclear NMR Relaxation.

Histidine is a key amino-acid residue in proteins with unique properties engendered by its imidazole side chain that can exist in three different states: two different neutral tautomeric forms and a protonated, positively charged one with a pKa value close to physiological pH. Commonly, two or all three states coexist and interchange rapidly, enabling histidine to act as both donor and acceptor of hydrogen bonds, coordinate metal ions, and engage in acid/base catalysis. Understanding the exchange dynamics among the three states is critical for assessing histidine's mechanistic role in catalysis, where the rate of proton exchange and interconversion among tautomers might be rate limiting for turnover. Here, we determine the exchange kinetics of histidine residues with pKa values representative of the accessible range from 5 to 9 by measuring pH-dependent 15N, 13C, and 1H transverse relaxation rate constants for 5 nuclei in each imidazole. Proton exchange between the imidazole and the solvent is mediated by hydronium ions at acidic and neutral pH, whereas hydroxide mediated exchange becomes the dominant mechanism at basic pH. Proton transfer is very fast and reaches the diffusion limit for pKa values near neutral pH. We identify a direct pathway between the two tautomeric forms, likely mediated by a bridging water molecule or, in the case of high pH, hydroxide ion. For histidines with pKa 7, we determine all rate constants (lifetimes) involving protonation over the entire pH range. Our approach should enable critical insights into enzymatic acid/base catalyzed reactions involving histidines in proteins.

Synthesis of linear chitosan-block-dextran copolysaccharides with dihydrazide and dioxyamine linkers

Dihydrazide (ADH) and dioxyamine (PDHA) were assessed for their efficacy in coupling chitosan and dextran via their reducing ends. Initially, the end-functionalization of the individual polysaccharide blocks was investigated. Under non-reducing conditions, chitosan with a 2,5-anhydro-D-mannose unit at its reducing end exhibited high reactivity with both PDHA and ADH. Dextran, with a normal reducing end, showed superior reactivity with PDHA compared to ADH, although complete conversion with ADH could be achieved under reductive conditions with NaBH3CN. Importantly, the oxime bond in PDHA conjugates exhibited greater stability against hydrolysis compared to the hydrazone bond in ADH conjugates. The optimal block coupling method consisted in reacting chitosan with an excess of dextran pre-functionalized with PDHA. The copolysaccharides could be synthesized in high yields under both reducing and non-reducing conditions. This methodology was applied to relatively long polysaccharide blocks with molecular weight up to 14,000 g/mol for chitosan and up to 40,000 g/mol for dextran. Surprisingly, block copolysaccharides did not self-assemble at neutral or basic pH; rather, they precipitated due to hydrogen bonding between neutralized amino groups of chitosan. However, nanoparticles could be obtained through a nanoprecipitation approach.

Interfacial interactions of nanoscale zero-valent iron particles with clay minerals in the aquatic environments: Experimental and theoretical calculation study

The environmental transport and fate of nanoscale zero-valent iron particles (nZVI) in soil and groundwater can be altered by their hetero-aggregation with clay mineral particles (CMP). This study examines the interactions between bare or carboxymethyl cellulose (CMC)-coated nZVI with typical CMP, specifically kaolinite and montmorillonite. Methods include co-settling experiments, aggregation kinetic studies, electron microscopy, Derjaguin–Landau–Verwey–Overbeek (DLVO) and extended DLVO (EDLVO) energy analysis, and density functional theory calculations, focusing on the pH dependency of these interactions. The EDLVO theory effectively described the interactions between nZVI and CMP in aquatic environments. Under acidic conditions (pH 3.5), the interfacial interaction between bare nZVI and kaolinite is regulated by van der Waals forces, while complexation, van der Waals forces, and electrostatic attraction govern the interaction of bare nZVI with montmorillonite, primarily depositing on the SiO face. In contrast, the positively charged AlO face and edge of CMP are the main deposition sites for CMC-coated nZVI through hydrogen bonding, van der Waals forces, and electrostatic attraction. At neutral (pH 6.5) and alkaline (pH 9.5) conditions, both bare and CMC-coated nZVI predominantly attach to the AlO face and edge, facilitated by complexation or hydrogen bonding, alongside van der Waals forces. The attachment of CMC-coated nZVI to CMP surfaces shows reversible aggregation or deposition due to the steric repulsion from the CMC coating. These findings hold significant implications for the environmental applications and risk of nZVI.