Desolvation Inability of Solid Hydrates, an Alternative Expression for the Gibbs Free Energy of Solvation, and the Myth of Freeze-Drying.

The term "desolvation inability" is proposed in order to describe the alteration of the original chemical structure of a solute ("decomposition") prior to the solvent's full removal upon the heating of the solvate. This behavior has been sporadically reported; however, it is much more frequent, and it is the basis of various, seemingly unrelated, effects/processes, e.g., the vinegar syndrome of cellulose acetate cinematographic films, in thermal energy storage. An explanation and a criterion/index for the prediction of this behavior are provided based on the comparison of the Gibbs free energies of decomposition and desolvation. A new approach for the expression of the Gibbs free energy of desolvation is proposed by reversing the roles of the solute and solvent and by regarding water as the solute rather than as the solvent, while the solute is treated as a solid solvent. This approach results in lower solvation/desolvation Gibbs free energy values. Based on the above, the experimentally observed thermal behavior of three inorganic hydrates is predicted and explained. Theoretically and experimentally, it is supported that decomposition is possible at sub-zero (°C) temperatures and the regarded simultaneous drying and protection of heat-sensitive substances by freeze-drying, at least in some cases, e.g., for the case of gallic acid, is an unverified myth.

Data on searching for synergy between alcohol and salt to produce more potent and environmentally benign gas hydrate inhibitors.

In order to systematically study the synergistic effect of gas hydrate inhibition with mixtures of methanol (MeOH) and magnesium chloride (MgCl2), the impact of these compounds on the thermodynamic stability of methane hydrate in the systems of CH4-MeOH-H2O, CH4-MgCl2-H2O, and CH4-MeOH-MgCl2-H2O was experimentally investigated. The pressure and temperature conditions of the three-phase vapor-aqueous solution-gas hydrate equilibrium were determined for these systems. The resulting dataset has 164 equilibrium points within the range of 234-289 K and 3-13 MPa. All equilibrium points were measured as the endpoint of methane hydrate dissociation during the heating stage. The phase boundaries of methane hydrate were identified for 8 systems with MeOH (up to 60 mass%), 5 MgCl2 solutions (up to 26.7 mass%), and 14 mixtures of both inhibitors. Most equilibrium points were measured using a ramp heating technique (0.1 K/h) under isochoric conditions when the fluids were stirred at 600 rpm. It was found that even a 0.5 K/h heating rate for the CH4-MgCl2-H2O system at low salt concentrations, along with all mixed aqueous solutions with methanol, gives results that do not differ from 0.1 K/h, considering the measurement uncertainties. Most measurements for the CH4-MgCl2-H2O system at high salt content were acquired using a step heating technique. The coefficients of the empirical equations approximating the equilibrium points for each inhibitor concentration were defined. The change in the slope parameter of the empirical equation was analyzed as a function of inhibitor content. Correlations that accurately describe the thermodynamic inhibition effect of methane hydrate with methanol and magnesium chloride on a mass% and mol% scale were obtained. The freezing temperatures of single and mixed aqueous solutions of methanol and magnesium chloride were determined experimentally to confirm the thermodynamic consistency of the methane hydrate equilibrium data.

Activation of Coq6p, a FAD Monooxygenase Involved in Coenzyme Q Biosynthesis, by Adrenodoxin Reductase/Ferredoxin.

Adrenodoxin reductase (AdxR) plays a pivotal role in electron transfer, shuttling electrons between NADPH and iron/sulfur adrenodoxin proteins in mitochondria. This electron transport system is essential for P450 enzymes involved in various endogenous biomolecules biosynthesis. Here, we present an in-depth examination of the kinetics governing the reduction of human AdxR by NADH or NADPH. Our results highlight the efficiency of human AdxR when utilizing NADPH as a flavin reducing agent. Nevertheless, akin to related flavoenzymes such as cytochrome P450 reductase, we observe that low NADPH concentrations hinder flavin reduction due to intricate equilibrium reactions between the enzyme and its substrate/product. Remarkably, the presence of MgCl2 suppresses this complex kinetic behavior by decreasing NADPH binding to oxidized AdxR, effectively transforming AdxR into a classical Michaelis-Menten enzyme. We propose that the addition of MgCl2 may be adapted for studying the reductive half-reactions of other flavoenzymes with NADPH. Furthermore, in vitro experiments provide evidence that the reduction of the yeast flavin monooxygenase Coq6p relies on an electron transfer chain comprising NADPH-AdxR-Yah1p-Coq6p, where Yah1p shuttles electrons between AdxR and Coq6p. This discovery explains the previous in vivo observation that Yah1p and the AdxR homolog, Arh1p, are required for the biosynthesis of coenzyme Q in yeast.

The Use of Isoflurane and Adjunctive Magnesium Chloride Provides Fast, Effective Anaesthetization of Octopus vulgaris.

A wide variety of substances have been used to anaesthetise invertebrates, but many are not anaesthetics and merely incapacitate animals rather than preventing pain. In essence, the role of an ideal general anaesthetic is to act as a muscle relaxant, an analgesic, an anaesthetic, and an amnesic. To achieve all these properties with a single substance is difficult, and various adjuvants usually need to be administered, resulting in a cocktail of drugs. In a clinical setting, the vast majority of patients are unaware of surgery being carried out and have no memory of it, so they can claim to have felt no pain, but this is much more difficult to demonstrate in invertebrates. Here, we show that 1% MgCl2, a muscle relaxant, is a useful adjuvant for the clinical anaesthetic isoflurane on Octopus vulgaris when applied alone in seawater for 10 min before the clinical anaesthetic. After this, full anaesthesia can be achieved in 5 min using 1% isoflurane insufflated into the saline still containing MgCl2. Full recovery takes place rapidly in about 10 to 15 min. The depth of anaesthesia was monitored using changes in respiratory rate, chromatophore pattern, and withdrawal movements of the arms and siphon. This methodology reduces stress on the animal and minimises the quantity of anaesthetic used.

Modelling and simulation of chemical reaction of porous MgCl2 pellets with NH3 by including impact of heat and mass transfer and structure change.

The MgCl2-NH3 reactive system is investigated in terms of heat and mass transfer coupled with chemical reaction through numerical simulation. The reversible nature of the chemical reaction is captured by including adsorption and desorption terms in the rate expression simultaneously. The kinetic coefficients of the adsorption are directly adopted from the literature, while those for the desorption reaction are calculated based on the thermodynamic relations. The impact of changing pressure and pellet porosity are also investigated in the simulations. The initial temperature of the pellet is 300 K in all simulations. Temperature, NH3 pressure, and conversion distributions in the pellets, along with pellet swelling are obtained and presented as a function of time. The results indicated strong effects of heat transfer resistances in the pellets.

Effect of MgCl2 Loading on the Yield and Performance of Cabbage-Based Biochar.

Converting more CO2 absorbed by plant photosynthesis into biomass-activated carbon effectively reduces carbon emissions. In this study, we used a one-step preparation of biomass-activated carbon loaded with MgO nanoparticles to investigate the effect of Mg loading on the catalytic pyrolysis process. The influences of magnesium loading on biochar yield and fixed carbon production were assessed. The addition of 1% Mg weakened the carbonyl C=O, inhibited the dehydroxylation reaction, enhanced the C-H signal strength, and the formation of MgO inhibited the weaker- bound substituent breakage. Additionally, the addition of magnesium altered the morphological features and chemical composition of the biochar material. It also increased the activated carbon mesoporosity by 3.94%, biochar yield by 5.55%, and fixed carbon yield by 12.14%. The addition of 1% Mg increased the adsorption capacity of the activated carbon to potassium dichromate, acid magenta, methylene blue, and tetracycline effluents by 8.71 mg, 37.15 mg, 117.68 mg, and 3.53 mg, respectively. The results showed that MgCl2 played a significant role in promoting the thermal degradation of biomass and improving the solid yield and adsorption performance of activated carbon.

High ionic strength dissociation assay reduces dimeric target interference in immunogenicity testing.

Aim: The presence of di-/multi-meric forms of soluble target in biological samples can interfere in anti-drug antibody (ADA) assays, leading to increased background values and potentially false positivity. The authors investigated the use of the high ionic strength dissociation assay (HISDA) to reduce target interference in two different ADA assays. Results: Interference caused by homodimeric FAP was successfully eliminated to enable cut point determination after applying HISDA. Biochemical experiments confirmed the dissociation of homodimeric FAP after treatment with high ionic strength conditions. Conclusion: HISDA is a promising approach to simultaneously achieve high drug tolerance and reduced interference by noncovalently bound dimeric target molecules in ADA assays without extensive optimization, which is particularly advantageous in routine use.

A Method to Replace NaCl as a Flotation Solution for Extracting MPs in Soil: A Case Study of the Jiaxing Agricultural Soil from China.

Microplastics (MPs) have become an important global issue in recent years. However, MPs in the soil have received far less attention than water. Effective and nondestructive extraction of MPs is important for studying MPs in agricultural soils. This study uses different floatation solutions as experiments and uses MgCl2 as the floatation solution of the density extraction method. Five types of standard MPs (PE, PP, PS, PVC, and PET) are used as the objects of this experiment. The recovery of the two particle sizes was between 90.82% and 109.69%. The extracted standard MPs were then subjected to IR and Raman spectroscopic analysis, and the results showed that Raman spectroscopy was more suitable for the identification of the extracted MPs. Finally, this method collected and verified a vast number of soil samples and further analyzed the abundance and characteristics of the collected MPs.

Cation Composition Influences the Toxicity of Salinity to Freshwater Biota.

The effects of salinization on freshwater ecosystems have been estimated by testing sodium chloride (NaCl) since it is the most widely used salt as a deicing agent and Na+ and Cl- ions are the most representative in seawater composition. However, calcium, magnesium, and/or potassium are starting to be proposed as potential surrogates for NaCl, but for which ecotoxicological effects are less explored. This study aimed to identify (i) the less toxic salt to freshwater biota to be suggested as a safer alternative deicer and (ii) to contribute to the lower tiers of salinity risk assessment frameworks by identifying a more suitable surrogate salt than NaCl. The battery of ecotoxicity assays with five key trophic level species showed that among the tested salts (MgCl2, CaCl2, and KCl), KCl and CaCl2 seemed to induce the highest and lowest toxicity, respectively, compared with NaCl. CaCl2 is suggested as a safer alternative for use as a deicer and KCl as a surrogate for the risk assessment of seawater intrusion in coastal regions. These results enrich the salt toxicity database aiming to identify and propose more suitable surrogate salts to predict the effects of salinization to a broader extent.

An improved approach of salting-out solvent-free microwave mediated rotary distillation for essential oil preparation from fresh leaves of magnolia (Oyama sieboldii).

An improved method denoted as salting out-solvent-free microwave rotary distillation (SOSFMRD) was successfully developed for the extraction of essential oils from fresh magnolia (Oyama sieboldii) leaves, in which we achieved the rotation of the reaction material by means of a rotating motor to subject the material to uniform microwave irradiation. Magnesium chloride was selected as the salting-out agent through a comparative study on the salting-out effects of different anions and cations of metal salts. The variables of SOSFMRD were systematically optimized. Under the obtained optimization conditions, the essential oil yield was 21.68 ± 1.02 mL/kgDW. Gas chromatography-mass spectrometry analysis showed that the main chemical constituent of O. sieboldii essential oil was dehydrocostuslactone, the content of which reached 30.23 ± 1.27 %. Compared with the other conventional methods, this method has a high yield and low energy consumption, which can effectively reduce impact on the environment.

A pilot investigation of the efficacy and safety of magnesium chloride and ethanol as anesthetics in Loligo vulgaris embryos.

The inclusion of cephalopods in the legislation related to the use of animals for experimental purposes has been based on the precautionary principle that these animals have the capacity to experience pain, suffering, distress, and lasting harm. Recent studies have expanded this view and supported it. Handling cephalopod mollusks in research is challenging and whenever more invasive procedures are required, sedation and/or anesthesia becomes necessary. Therefore, finding adequate, safe, and effective anesthetics appears mandatory. Several substances have been considered in sedating cephalopods, in some instances applying those utilized for fish. However, species-specific variability requires more detailed studies. Despite long-lasting experience being linked to classic studies on squid giant axons, evidence of action on putative anesthetic substances is scarce for Loligo vulgaris and particularly for their embryos. The aim of the current study was to evaluate effects elicited by immersion of squid embryos in anesthetic solutions and examine whether these forms display a similar reaction to anesthetics as adults do. Different concentrations of ethanol (EtOH; 2, 2.5, and 3%) and magnesium chloride (MgCl2; 1, 1.5, and 1.8%) were tested by adopting a set of indicators aimed at exploring the physiological responses of squid embryos. Forty-two embryos of the common squid Loligo vulgaris (stages 27-28) were assigned to three conditions (EtOH, MgCl2, and controls) and video recorded for 15 min (5 min before, 5 min during, and 5 min after immersion in the anesthetic solutions). In each group, the heart rate, respiratory rate, buoyancy, chromatophore activity, and tentacles/arms responses were assessed to evaluate the embryos' vitality and responsiveness to stimulation. Both substances provoked a decrease in heart and respiratory rates and inhibited buoyancy, chromatophores, and tentacles/arms responses; no adverse effects were observed. EtOH had a faster onset of action and faster recovery than MgCl2, being potentially more adequate as an anesthetic for shorter procedures. Even though MgCl2 caused a longer muscle relaxation, the reversibility was not confirmed for the 1.8% concentration; however, lower concentrations triggered similar results as the ones obtained with the highest EtOH concentrations. We have shown that the late developmental stages of Loligo vulgaris embryos could represent a good model to evaluate anesthetics for cephalopods since they can display similar reactions to anesthetics as adults animals do.

Osmoprotectants boost adaptation and protect methanogenic microbiome during ammonia toxicity events in continuous processes.

Different osmoprotectants were used to counteract ammonia toxicity in continuous anaerobic reactors. The anaerobic microbiome osmoadaptation process and its role to the methanogenic recovery are also assessed. Three osmoprotectants (i.e., glycine betaine, MgCl2 and KCl) were respectively introduced in continuous reactors at high ammonia levels, namely RGB, RMg, RK, while a control reactor (RCtrl) was also used. After ammonia was introduced, the RGB, RMg, RK and RCtrl suffered 39.0%, 36.6%, 39.9% and 36.2% methane production loss, respectively. Osmoprotectants addition recovered significantly methane production by up to 68.9%, 54.3% and 32.2% for RGB, RMg and RK, respectively contrary to RCtrl, where production increased only by 13.6%. The recovered methane production was maintained in RGB and RMg for at least four HRTs, even after the addition of osmoprotectants was stopped, due to the formed methanogenic microbiota by osmoadaptation process, with Methanoculleus sp. as the dominant species.

Magnesium Potentiates the Vortioxetine's Effects on Physical Performances and Biological Changes in Exercise-Induced Stress in Rats.

Background and objectives: Vortioxetine (VRT) is a relatively new selective serotonin reuptake inhibitor (SSRI) antidepressant and serotonin receptor modulator, approved for the treatment of major depression and generalized anxiety disorder. Depression has been linked with psychomotor disengagement, oxidative stress burden and decreased blood levels of brain-derived neurotrophic factor (BDNF). In our study we performed the experimental investigation of VRT, magnesium and of their association on the rats' endurance capacity, motor behavior and blood biological disturbances in rats subjected to forced exercise in treadmill test. Materials and Methods: The substances were administered orally for 14 consecutive days, as follows: group 1 (control): distilled water 0.3 mL/100 g body; group 2 (Mg): magnesium chloride 200 mg/kg body; group 3 (VRT): VRT 20 mg/kg body; group 4 (VRT+Mg): VRT 20 mg/kg body + magnesium chloride 200 mg/kg body. Magnesium was used as positive control substance with known effects in treadmill test. The consequences of VRT treatment on glucose, cortisol, BDNF and oxidative stress biomarkers (superoxide-dismutase, malondialdehyde, glutathione-peroxidase, lactate dehydrogenase) were also assessed. Results and conclusions: The use of VRT resulted in an improvement in motor capacity and an increase of the rats' endurance to physical effort. The administration of VRT increased the serum BDNF levels and reduced the oxidative stress in rats subjected to physical effort. The association of magnesium potentiated the effects of VRT on physical performances, the antioxidant activity and the decreasing in serum stress markers in treadmill test in rats.

Durability of concretes exposed to high concentrations of CaCl2 and MgCl2.

In cold regions, calcium and magnesium chloride deicing salts damage concrete pavements due to the formation of certain deleterious chemical phases, including calcium oxychloride. While there is much research at a cement paste-scale, damage in concrete has been less studied. In this study, we evaluate concrete damage due to calcium and magnesium chloride and explain the roles of supplementary cementitious materials (SCM) replacement level, air entrainment, salt type, and exposure conditions in damage development. Various non-destructive test methods including bulk resistivity, mass change, and visual damage assessment were used to monitor the damage over time. Damage was reduced as the SCM replacement level and air content increased, regardless of exposure conditions. Bulk resistivity and visual assessment were promising indicators of damage. The product of 91-day bulk resistivity and the air content predicted concrete performance when exposed to concentrated deicing salts. Based on several criteria, mixtures with 20% fly ash replacement level or 35% slag mitigated damage significantly when the air content was greater than 5% by concrete volume. Damage mitigation mechanisms of SCM and air are discussed. Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-01992-y.

Ibuprofen Removal by Graphene Oxide and Reduced Graphene Oxide Coated Polysulfone Nanofiltration Membranes.

The presence of pharmaceutical products, and their metabolites, in wastewater has become a focus of growing environmental concern. Among these pharmaceutical products, ibuprofen (IBU) is one of the most consumed non-steroidal anti-inflammatory drugs and it can enter the environment though both human and animal consumption, because it is not entirely absorbed by the body, and the pharmaceutical industry wastewater. Nanofiltration has been described as an attractive process for the treatment of wastewater containing pharmaceutical products. In this paper, the modification of a polysulfone nanofiltration membrane by coating with graphene oxide (GO) and reduced graphene oxide (RGO) has been carried out. The morphology and elemental composition of the active layer of unmodified and modified membranes were analyzed by scanning electronic microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX), respectively. Initial characterization membranes was carried out, studying their water permeability coefficient and their permeate flux and rejection coefficients, at different applied pressures, using magnesium chloride solutions. The behavior of both pristine and coated membranes against ibuprofen solutions were analyzed by studying the permeate fluxes and the rejection coefficients at different pressures and at different contaminant concentrations. The results have shown that both GO and RGO coated membranes lead to higher values of ibuprofene rejection than that of uncoated membrane, the latter being the one that presents better results in the studies of permeability, selectivity, and fouling.

Comparative study of the antioxidant activity of the essential oils of five plants against the H2O2 induced stress in Saccharomyces cerevisiae.

The purpose of this work was to investigate the protective effect of five essential oils (EOs); Rosmarinus officinalis, Thymus vulgaris, Origanum compactum Benth., Eucalyptus globulus Labill. and Ocimum basilicum L.; against oxidative stress induced by hydrogen peroxide in Saccharomyces cerevisiae. The chemical composition of the EOs was analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC/MS). The in vitro antioxidant activity was evaluated and the protective effect of EOs was investigated. Yeast cells were pretreated with different concentrations of EOs (6.25-25 µg/ml) for an hour then incubated with H2O2 (2 mM) for an additional hour. Cell viability, antioxidants (Catalase, Superoxide dismutase and Glutathione reductase) and metabolic (Succinate dehydrogenase) enzymes, as well as the level of lipid peroxidation (LPO) and protein carbonyl content (PCO) were evaluated. The chemical composition of EOs has shown the difference qualitatively and quantitatively. Indeed, O. compactum mainly contained Carvacrol, O. basilicum was mainly composed of Linalool, T. vulgaris was rich in thymol, R. officinalis had high α-Pinene amount and for E. globulus, eucalyptol was the major compound. The EOs of basil, oregano and thyme were found to possess the highest amount of total phenolic compounds. Moreover, they have shown the best protective effect on yeast cells against oxidative stress induced by H2O2. In addition, in a dose dependent manner of EOs in yeast medium, treated cells had lower levels of LPO, lower antioxidant and metabolic enzymes activity than cells exposed to H2O2 only. The cell viability was also improved. It seems that the studied EOs are efficient natural antioxidants, which can be exploited to protect against damages and serious diseases related to oxidative stress.

Exploration of the process and mechanism of magnesium chloride induced starch gelatinization.

As a new starch gelatinization method, salt induced gelatinization can not only reduce energy consumption but also impart special physicochemical properties to starch gel. In this study, the process and mechanism of MgCl2 induced starch gelatinization were explored. The results showed that, potato starch could be gelatinized after a treatment of 4 mol/L MgCl2 for 3 h. The gelatinization started with the slight damage of outer shells, then the internal molecules leached out through the cracks or holes to form gel, finally the outer shells disintegrated. During the gelatinization process, the viscosity and granule size gradually increased after 0.5 h, while the original crystallinity disappeared rapidly in 0.5 h. Besides, MgCl2 significantly increased the electrostatic interaction, then made starch molecules closer to each other and become denser, which may have close relationship with the appearance of the cracks and the disappearance of crystallization. Moreover, MgCl2 enhanced the hydration and increased the binding free energy of starch molecules, then promoted starch gelatinization and accelerated the destruction of starch structure, which may be the critical factors of the starch gelatinization induced by MgCl2. The results will provide reference for the research and application of salt induced gelatinization.

Dynamic elution of residual ammonium leaching agent from weathered crust elution-deposited rare earth tailings by magnesium chloride.

The release of residual ammonium (RA) leaching agent from weathered crust elution-deposited rare earth tailings would cause serious environmental pollution, and it was necessary to efficiently remove it from the ore body before the mine closure. In this study, occurrence states of the RA were determined and dynamic elution of RA from rare earth tailings by using magnesium chloride as eluent was investigated. Effects of initial concentration, pH, flow rate, and particle size on the ammonium removal efficiency were investigated, and variations of ammonium occurrence states before and after elution were determined. Lastly, elution mechanism was discussed. Results showed that removal efficiency of RA by magnesium chloride was significantly higher than that by deionized water, and elution efficiency of RA could reach about 95.7% at the optimum laboratory experiment conditions. Energy dispersive spectrometer (EDS) analysis illustrated that the residual ammonium was replaced by Mg2+ during the elution process, and occurrence state experimental results showed that 94.0% of water-soluble and adsorbable ammonium was eluted. The empirical kinetic equation of eluting RA by magnesium chloride was established as 1-2/3α-(1-α)2/3= 0.02*C00.6t. This study provided a valuable method for reducing environmental pollution caused by the release of the residual ammonium from the rare earth tailings.

Evaluation of the anti-biofilm activities of bacterial cellulose-tannic acid-magnesium chloride composites using an in vitro multispecies biofilm model.

Chronic wounds are a serious worldwide problem, which are often accompanied by wound infections. In this study, bacterial cellulose (BC)-based composites introduced with tannic acid (TA) and magnesium chloride (BC-TA-Mg) were fabricated for anti-biofilm activities. The prepared composites' surface properties, mechanical capacity, thermal stability, water absorption and retention property, releasing behavior, anti-biofilm activities and potential cytotoxicity were tested. Results showed that TA and MgCl2 particles closely adhered to the nanofibers of BC membranes, thus increasing surface roughness and hydrophobicity of the membranes. While the introduction of TA and MgCl2 did not influence the transparency of the membranes, making it beneficial for wound inspection. BC-TA and BC-TA-Mg composites displayed increased tensile strength and elongation at break compared to pure BC. Moreover, BC-TA-Mg exhibited higher water absorption and retention capacity than BC and BC-TA, suitable for the absorption of wound exudates. BC-TA-Mg demonstrated controlled release of TA and good inhibitory effect on both singly cultured Staphylococcus aureus and Pseudomonas aeruginosa biofilm and co-cultured biofilm of S. aureus and P. aeruginosa. Furthermore, the cytotoxicity grade of BC-TA-6Mg membrane was eligible based on standard toxicity classifications. These indicated that BC-TA-Mg is potential to be used as wound dressings combating biofilms in chronic wounds.