Our recent study demonstrated that fulvic and humic acids are the major contributors to the adsorption of phenoxyalkanoic acid herbicides in soils. At very low pH, the neutral forms of these herbicides are bound directly to fulvic and humic acids, whereas at higher pH, their anionic forms are adsorbed mainly via bridges created by Al3+ species. The number of active sorption sites associated with Al3+ species complexed with fulvic acids is pH-dependent, whereas the number of corresponding sites in humic acids is pH-independent. Based on the results of the FTIR analysis, research into adsorption thermodynamics, and molecular modeling, an attempt was made in the present study to explain the adsorption mechanisms of six phenoxyalkanoic herbicides used currently in the European Union on the surfaces of the above fractions of humic substances. The obtained values of standard enthalpy (ΔH0) for the adsorption of the anionic forms of phenoxyalkanoic herbicides on fulvic or humic acids complexed with Al3+ were in the range of physical adsorption, i.e. from -8.4 kJ/mol to -2.9 kJ/mol for the former, and from -5.3 kJ/mol to -2.4 kJ/mol for the latter. The study demonstrated that the neutral forms of phenoxyalkanoic herbicides were bound to humic substances mainly via H-bonds, π-π stacking interactions, and hydrophobic interactions. Al3+ species were complexed with fulvic and humic acids to form outer-sphere complexes. Ternary outer-sphere complexes were also created between the anionic forms of phenoxyalkanoic acid herbicides and positively charged Al3+ species complexed with fulvic acids. The mechanisms of adsorption on humic acids involved a ligand exchange between a loosely bound hydroxyl group of hydrolyzed Al3+ complexed with this adsorbent and the anionic form of the herbicide. However, in this case, adsorption took place only in the presence of sufficiently strong hydrophobic and π-π stacking interactions supported by H-bonds. These findings elucidate why phenoxyalkanoic herbicides are mobile in the soil profile and are often rapidly degraded in soils.

The removal of harmful arsenic(V) from aqueous solutions using Cyanex 923 (solvation extractant) was investigated under various experimental variables: equilibration time, acidity of the aqueous phase, temperature, extractant and arsenic concentrations, and O/A ratio. Cyanex 923 extracted As(V) (and sulphuric acid) from acidic solutions, thus, its use to remove the metal from slightly acid or neutral solutions it is not possible. Extraction of arsenic is exothermic, and responded to the formation of H3AsO4·nL species in the organic phase (L represented the extractant and the stoichiometric factor n: 1 or 2, depends on the acidity of the aqueous phase). Extraction isotherms are derived from experimental results. Both arsenic and sulphuric acid loaded onto the organic phase can be stripped with water, and stripping isotherms are also derived from the experimental results. The selectivity of the system against the presence of other metals (Cu(II), Ni(II), Bi(III), Sb(III)) are investigated, and also it is investigated the ability of Cyanex 923 to extract As(V) and sulphuric acid against the use of other P=O based solvation reagents, such dibutyl butylphosphonate (DBBP) and tri-butyl phosphate (TBP).

The preservative qualities of individual ionic compounds on the infectivity of T4 virions were elucidated. T4 virions were immersed in quasi-pure ionic solutions prior to the adsorption process, and the pfu values of these were measured following the conventional method. In neutral ionic solutions, the minimum and the optimum concentrations for preservative qualities were corresponded with the results obtained from the multi-ionic media/buffers. In acid and alkali solutions, phages show tolerances at a pH range of 5-11 in multi-ionic media/buffers. T4 virions show no tolerance in quasi-pure acid, neutral and weak alkaline conditions. The preservative quality of T4 virions was jumped up in over 10-1 mM OH- solution, equivalent to pH value over 10, which is corresponding to the pKa of the deprotonation of the DNA bases G and T. Infectivity was lost below 10-1 mM OH- and higher than 10 mM OH-. These results implicate the maintaining of infectivity of a virion may need the flexibility of the intra-capsid DNA by deprotonation.

Spent batteries recycling is an important way to obtain low-cost graphite. Nevertheless, the obtaining of crystalline graphite with a rather low density of defects is required for many applications. In the present work, high-quality graphites have been obtained from different kinds of spent batteries. Black masses from spent alkaline batteries (batteries black masses, BBM), and lithium-ion batteries from smartphones (smartphone black masses, SBM) and electric and/or hybrid vehicles (lithium-ion black masses, LBM) were used as starting materials. A hydrometallurgical process was then used to obtain recycled graphites by acidic leaching. Different leaching conditions were used depending on the type of the initial black mass. The final solids were characterized by a wide set of complementary techniques.

Aquaculture by-products can be compromised an important liming material of increasing soil pH and soil fertility. The aim of this research was to assess the effect of mussel shells on soil pH, on organic matter and on soil nutrients. In this study a pot experiment was carried out at the De-partment of Ichthyology and Aquatic Environment (University of Thessaly, Greece). A acidic soil (pH 4.26) amended with 6 different proportions of mussel shell (0.0, 0.1, 0.3, 0.5, 1, 3 and 6%) in two different grain sizes (Fine powder (>1 mm) and Coarse powder (1-2 mm)), resulting in 13 treatments. According to the results, it was observed that pH, organic matter, Available P and Exchangeable K increased. Specifically, the highest pH values observed at 6% rate. Available P and Exchangeable K achieved the highest content at 6% Fine powder treatment, 46.2 and 190.1 mg kg-1, respectively. Similarly, organic matter had the highest value in 6% Fine powder pots (2.27%). Moreover, Total N concentration varied from 0.11 to 0.14 but no statistically significant different was noticed between the treatments. In conclusion, mussel shells can compose a promising liming material in the agriculture section.

Myotoxic phospholipases A₂ are responsible for many clinical signs in envenomation by Bothropssnakes. A new myotoxic acidic PLA₂ Asp 49 was isolated from Colombian Bothrops asper venom. It was isolated by high efficiency liquid chromatography and named BaCol PLA₂. It had a molecular weight of 14180.69 Da and an isoelectric point of 4.4. The complete sequenceobtained by cDNA cloning, with access number in the gene bank MF319968; this sequenceevidenced a mature product of 124 amino acids with Asp in 49 position. In vivoassaysin mice demonstrated profuse oedemaand myotoxicity evidenced by increase of creatinakinasa in plasma and severe and diffuse damage to the muscular fibers, further vacuolization and hyalinization necrosis of the sarcoplasm showed by histopathology with hematoxylin and eosin staining of gastrocnemius muscle. In vitro studies showed cell membrane damage without phosphatidylserine exposure, an early apoptosis hallmark. Further BaCol PLA₂ evidenced high indirect hemolytic activityand moderate anticoagulant action. The toxin showed homology with others acidic PLA₂ isolated from Bothrops venoms, including one isolated from B. asper of Costa Rica. Unlike this, BaCol PLA₂ was myotoxic.

Background: Stroke is one of the leading causes of death and disability worldwide. The diagnosis of stroke remains largely clinical, yet widely used stroke scoring systems and brain imaging do not satisfactorily allow distinction of ischaemic stroke (IS) patients from stroke mimics (SM). Blood biomarkers are promising tools that could facilitate clinical triage. Methods: This study recruited 66 patients with IS and 24 SM. The levels of Glial fibrillary acidic protein (GFAP), Neuron-specific enolase (NSE), Neurofilament light chain (NfL) and blood-brain barrier (BBB) proteins [Occludin (OCLN), Zonula occludens 1 (ZO-1), Claudin-5] in blood serum were measured by enzyme-linked immunosorbent assay technique. Biomarker levels in IS patients and SM was compared using the Mann–Whitney U test. Multivariable logistic regression analysis was used to evaluate the diagnostic performance of biomarkers in combination with the National Institutes of Stroke Scale (NIHSS) score. Results: Significant differences in circulating GFAP, NfL, OCLN, ZO-1, and Claudin-5 but not NSE in IS patients compared to SM. The combination of circulating ZO-1, Claudin-5, and OCLN with NIHSS score gives the highest diagnostic accuracy, sensitivity, and specificity. Conclusion: A prediction model with Circulating BBB proteins in combination with NIHSS score differentiates between IS patients and SM.

As the global energy crisis continues, efficient hydrogen production is one of the hottest topics these days. In this sense, establishing catalytic trends for hydrogen production is essential for choosing proper H2 generation technology and catalytic material. Volcano plots for hydrogen evolution in acidic media are well-known, while volcano plot in alkaline media was constructed ten years ago using theoretically calculated hydrogen binding energies. Here we show for the first time that the volcano-type relationships are largely maintained in a wide range of pH values, from acidic to neutral and alkaline solutions, using theoretically calculated hydrogen binding energies on clean metallic surfaces and experimentally measured hydrogen evolution overpotentials. If metallic surfaces are exposed to high anodic potentials, hydrogen evolution can be boosted or significantly impeded, depending on the metal and the electrolyte in which the reaction occurs. Such effects are discussed here and can be used to properly tailor catalytic materials for hydrogen production via different water electrolysis technologies.

The pH dependence of the free energy level of the flash induced primary charge pair P+IA– was determined by combination of the results from indirect charge recombination of P+QA– and from delayed fluorescence of the excited dimer (P*) in reaction center of photosynthetic bacterium Rhodobacter sphaeroides where the native ubiquinone at the primary quinone binding site QA was replaced by low potential anthraquinone derivatives. The following observations were made: 1) The free energy state of P+IA– was pH independent below pH 10 (–370 ± 10 meV relative to that of the excited dimer P*) and showed remarkable decrease (about 20 meV/pH unit) above pH 10. A not insignificant part of the dielectric relaxation of the P+IA– charge pair (about 120 meV) should come from protonation related changes. 2) The single exponential decay character of the kinetics proves that the protonated/unprotonated P+IA– and P+QA– states are in equilibria and the rate constants of protonation konH +koffH is much larger than that of the charge back reaction kback ~103 s-1. 3) Highly similar pH profiles were measured for the free energy states of P+QA– and P+IA–, indicating that the same acidic cluster around QB should response to both anionic species. This was supported by model calculations based on anticooperative proton distribution in the cluster with key residues of GluL212, AspL213, AspM17 and GluH173 and on effect of polarization of the aqueous phase on the electrostatic interaction. The larger distance of IA– from the cluster (25.2 Å) than that of QA‒ (14.5 Å) is compensated by smaller effective dielectric constant (6.5 ± 0.5 and 10.0 ± 0.5, respectively). 4) The P* → P+QA− and IA‒QA → IAQA− electron transfers are enthalpy driven reactions with exemption of very large (>60%) or negligible entropic contributions in cases of substitution by 2,3-dimethyl-AQ or 1-chloro-AQ, respectively. The possible structural consequences are discussed.

Background & Objective. Perinatal hypoxia acutely triggers the release of cytokines and chemokines from neurons, astrocytes and microglia. In response to hypoxia-ischemia resting/ramified microglia proliferate and undergo activation, with the production of proinflammatory molecules. The brain damage extension seems to be related with both the severity of hypoxia and the balance between pro and anti-inflammatory host response. Methods: In this preliminary study we compared in 10 neonates with hypoxic ischemic encephalopathy (HIE), during therapeutic hypothermia (TH), plasmatic cytokines and other inflammatory molecules levels: monocytic chemotactic-protein-1 (CCL2/MCP-1), CXCL8, glial fibrillary acidic protein (GFAP), Interferon gamma (IFN y), Interleukin 10 (IL-10), IL-18, IL-6, CCL3, ENOLASE2, Colony Stimulating Factor(GM-CSF), IL-1b, IL-12p70, IL-33, Tumor Necrosis Factor alpha(TNF), collected at four different time points during TH (24 hours, 25-48 hours, 49-72 hours) , and after the rewarming (7-10 days from birth). Five of enrolled babies had pathological brain MRI (“cases”) and 5 had a normal examination (“controls”). Cytokines were measured by Magnetic Luminex Assay (Luminex SV 013-17 (14), instrument Biorad Bio-Plex 100 s.n. LX 10005039304). MRI images were classified according to the Barkovich score. Results: Mean levels of all cytokines and molecules at time T1 were not significantly different in the two groups of patients. Comparing samples paired by day of collection, the greatest differences between cases and controls were found at times T2 and T3, during TH. After rewarming, some molecules showed an upward trend. At T4, levels tended to be close again (with the exception of IL-6, IL10 and IL18). Infants with worse MRI showed plasmatic GFAP levels higher than those with normal MRI, while their IL-18 was lower. Mean levels of CCL3MIP1alpha, GMCSF, IL1BETA overlapped throughout the observation period in both the groups of neonates. Conclusion. In children with worse brain MRI we found high levels of GFAP and of IL-10 at T4, considered respectively an early biomarker of brain damage and a predictor of adverse outcome, according to the literature, and a trend towards low IL-18 levels. We found the greatest, although not significant, difference between molecules levels in cases and controls at time points T2 and T3, during TH. With the rewarming some molecules showed an upward trend. We cannot exclude that the small sample size may prevent significance in the differences from being achieved.

Proton exchange membrane water electrolyzers (PEMWEs) for water electrolysis have received tremendous attention due to their immediate response, high proton conductivity, low ohmic losses and gas crossover rate. However, design high activity, economical and long-term durable electrocatalysts in an acidic environment is still the bottleneck to realize the large-scale commercialization of PEMWEs. Iridium-based materials represent one of the most promising classes of oxygen evolution reaction (OER) catalysts due to their intrinsic stability in acid media over ruthenium-based counterparts. However, only a few innovative approaches have been developed to synthesizing iridium-based catalysts (IBCs) in the past decade, mainly due to achieving high activity may deteriorate the stability of IBCs. Accordingly, various engineering strategies of optimizing IBCs have been proposed to address this issue, including doping engineering, morphology engineering, crystal phase engineering and support engineering. Herein, a critical overview focusing on various synthesis and modulation strategies of IBCs is presented, based on an in-depth understanding of the relationship between electronic structures, charge redistribution and activity as well as stability of the electrocatalysts. In addition, the unprecedented achievements in PEMWEs are summarized. The reaction mechanisms and future perspectives are critically discussed to inspire more rational design of IBCs toward practical applications.

The effects of acidic electrolyzed water (AEW) on the microbiological and physicochemical properties of fresh-cut red cabbages were studied. The fresh-cut red cabbages and artificially inoculated red cabbages with Salmonella Typhimurium DT104 were washed with distilled water (DW) and different available chlorine concentration (ACC) of AEW for different times. AEW treatments significantly reduced the populations of native aerobic bacteria, molds and yeasts, and artificially inoculated S. Typhimurium DT104 compared to the DW treated and untreated red cabbage samples. The effectiveness of AEW treatments was greatly enhanced with increasing ACC and treatment times. S. Typhimurium DT104 were not detected in the washing water after the red cabbages treated by AEW. The surface color, pH, and total phenolic contents were did not significantly change when the red cabbages were washed with DW and 100 ppm AEW for 3 min. The anthocyanin contents and antioxidant activities of red cabbage were significantly reduced by 18.5% for cyanidin, 22.1% for pelargonidin, and 11.2% for DPPH radical scavenging activity, the impacts on the nutritional benefits of red cabbage were considered as limited and acceptable. The optimal process condition of AEW for washing red cabbage was 100 ppm for 3 min. In these conditions, most of the native microflora were inactivated, and artificial inoculated S. Typhimurium DT104 on the red cabbage were reduced by 40.2% (3.67 log CFU/g) and with minimal losses of nutrients and antioxidant activity, as well as no requirement of discontinuation treatment on the washing water.

The widespread use of epoxy resin (ER) in industry, owing to its excellent properties, aligns with the global shift toward greener resources and energy-efficient solutions, where utilizing metal oxides in 3D printed polymer parts can offer extended functionalities across various industries. ZnO concentrations in polyurethane acrylate composites impacted adhesion and thickness of DLP samples, with 1 wt.% achieving a thickness of 3.99±0.16 mm, closest to the target thickness of 4 mm, while 0.5 wt.% ZnO samples exhibited the lowest deviation in average thickness (±0.03 mm). Tensile strength in digital light processed (DLP) composites with ZnO remained consistent, ranging from 23.29 MPa (1 wt.%) to 25.93 MPa (0.5 wt.%), with an increase in ZnO concentration causing a reduction in tensile strength to 24.04 MPa and a decrease in the elastic modulus to 2001 MPa at 2 wt.% ZnO. The produced DLP samples, with their good corrosion resistance in alkaline environments, are well-suited for applications as protective coatings on tank walls. Customized DLP techniques can enable their effective use as structural or functional elements, such as in Portland cement concrete walls, floors and ceilings for enhanced durability and performance.

Solid tumours are characterized by an altered microenvironment (TME) from the physi-cochemical point of view, displaying a highly hypoxic and acidic interstitial fluid. Hy-poxia results from uncontrolled proliferation, aberrant vascularization and altered can-cer cell metabolism. Tumour cellular apparatus adapt to hypoxia by altering its metab-olism and behaviour, increasing its migratory and metastatic abilities by acquisition of a mesenchymal phenotype and selection of aggressive tumour cell clones. Extracellular acidosis is considered a cancer hallmark, acting as a driver of cancer aggressiveness by promoting tumour metastasis and chemoresistance by selecting for more aggressive cell phenotypes, although the underlying mechanism is still not clear. In this context, Ca2+ channels represent good target candidates due to their ability to integrate signals from the TME. Ca2+ channels are pH and hypoxia sensors and alterations in Ca2+ homeostasis in cancer progression and vascularization have been extensively reported. The present review will focus on Ca2+ permeable ion channels, with a major focus on TRP, SOC and PIEZO channels, that are modulated by tumour hypoxia and acidosis as well as the role of the resulted altered Ca2+ signals on cancer progression hallmarks. A deeper compre-hension of the Ca2+ signaling and acidic pH/hypoxia interplay will break new ground for the discovery of alternative and attractive therapeutics targets.

Abstract: Supplementation of infant formula with ingredients potentially able to manage, in a way positive for the host, the gut microbiota of infants, is nowadays widely used by infant food producers. The impact of this class of compounds, named prebiotics, on gut microbiota composition, was initially measured on the enrichment of Bifidobacterium and Lactobacillus spp., but the use of culture-independent analytical techniques has allowed to establish that a larger number of intestinal microorganisms are affected by the ingestion of prebiotics. However, despite a relevant number of scientific publications, actually there is no consensus on the amount of prebiotics to be administered daily, the potentially different actions exerted by prebiotics which differ in biochemical structures, as well as the impact of different percentages of the same prebiotics when used in mixtures and/or combination. This paper is aimed to critically review the available data on the use of prebiotics in infant formula, with special attention paid to identify a link between, the dosage used, the mixture composition and the observed outcomes, keeping in mind the influences in nutrition quality and growth influence.

Water electrolysis provides efficient and cost-effective production of hydrogen from renewable energy. Currently, the oxidation half-cell reaction relies on noble-metal catalysts, impeding widespread application. In order to adopt water electrolyzers as the main hydrogen production systems, it is critical to develop inexpensive and earth-abundant catalysts. This review discusses the proton exchange membrane (PEM) water electrolysis (WE) and the progress in replacing the noble-metal catalysts with earth-abundant ones. Researchers within this field are aiming to improve the efficiency and stability of earth-abundant catalysts (EACs), as well as to discover new ones. The latter is particularly important for the oxygen evolution reaction (OER) under acidic media, where the only stable and efficient catalysts are noble-metal oxides, such as IrO_x and RuO_x. On the other hand, there is significant progress on EACs for the hydrogen evolution reaction (HER) in acidic conditions, but how many of these EACs have been used in PEM WEs and tested under realistic conditions? What is the current status on the development of EACs for the OER? These are the two main questions this review addresses.