Stoichiometric Excess Research Articles

Reducing Stoichiometric Excess of Base to Catalytic Amount: Revisiting Staudinger Reaction for -lactam Synthesis

Background: -lactams have been primarily utilized as a leading class of effective antibiotics. They have been found to show activity against various diseases, prompting the scientific community to prioritise innovative protocols for their synthesis. The general and well-known synthetic strategy involves the classical Staudinger reaction exhibiting [2+2] cycloaddition reaction. However, the protocol utilizes stoichiometric excess of base for efficient product formation. Objective: A smarter and more acceptable approach for the synthesis of -lactams would be to reduce the excess base to a catalytic amount, furnishing a catalytic version of the Staudinger reaction. The modified version can eliminate the hazards arising out of excess use of the base, ultimately promoting the environmentally benign approach. Methods: With this hypothesis, a base-catalyzed approach in dimethyl formamide (DMF) towards the synthesis of -lactam via Staudinger reaction has been endorsed under moderate reaction conditions. Results: The scope of the substrates was explored with both electron-withdrawing and electronreleasing substitutions in the formation of -lactam. The reduction of the base amount from stoichiometric to catalytic amount was justified by the involvement of DMF in generating the basic condition for the reaction. Conclusion: It was hypothesized that the decomposition of DMF under the base-catalysed reaction condition can generate dimethylamine, which produces the required basic environment. conclusion: A base-catalysed approach in dimethyl formamide (DMF) towards the synthesis of β-lactam via Staudinger reaction has been endorsed under moderate reaction conditions. The substrates scope was explored with both electron withdrawing and electron releasing substitutions in the formation of β-lactam. The reduction of base amount from stoichiometric to catalytic was justified by the involvement of DMF in generating the basic condition for the reaction. It was hypothesized that the decomposition of DMF under the base catalysed reaction condition can generate dimethylamine which produces the required basic environment.

Chemical approaches to the sulfation of small molecules: current progress and future directions.

Sulfation is one of the most important modifications that occur to a wide range of bioactive small molecules including polysaccharides, proteins, flavonoids, and steroids. In turn, these sulfated molecules have significant biological and pharmacological roles in diverse processes including cell signalling, modulation of immune and inflammation response, anti-coagulation, anti-atherosclerosis, and anti-adhesive properties. This Essay summarises the most encountered chemical sulfation methods of small molecules. Sulfation reactions using sulfur trioxide amine/amide complexes are the most used method for alcohol and phenol groups in carbohydrates, steroids, proteins, and related scaffolds. Despite the effectiveness of these methods, they suffer from issues including multiple-purification steps, toxicity issues (e.g., pyridine contamination), purification challenges, stoichiometric excess of reagents which leads to an increase in reaction cost, and intrinsic stability issues of both the reagent and product. Recent advances including SuFEx, the in situ reagent approach, and TBSAB show the widespread appeal of novel sulfating approaches that will enable a larger exploration of the field in the years to come by simplifying the purification and isolation process to access bespoke sulfated small molecules.

Complexation Mechanisms of Aqueous Amylose: Molecular Dynamics Study Using 3-Pentadecylphenol.

Molecular dynamics (MD) simulations of linear amylose fragments containing 10 to 40 glucose units were used to study the complexation of the prototypical compound, 3-pentadecylphenol (PDP)─a natural product with surfactant-like properties─in aqueous solution. The amylose-PDP binding leverages mainly hydrophobic interactions together with excluded volume effects. It was found that while the most stable complexes contained PDP inside the helical structure of the amylose in the expected guest-host (inclusion) complexation manner, at higher temperatures, the commonly observed PDP-amylose complexes often involved more nonspecific interactions than inclusion complexation. In the case where a stoichiometric excess of PDP was added to the simulation box, self-aggregation of the small molecule precluded its ability to enter the internal helical part of the oligosaccharide, and as a result, inclusion complexation became ineffective. MD simulation trajectories were analyzed preliminarily using cluster analysis (CA), followed by more rigorous solvent accessible surface area (SASA) determination over the temperature range spanning from 277 to 433 K. It was found that using the SASA of PDP corrected for its intrinsic conformational changes, together with a generic hidden Markov model (HMM), an adequate quantification of the different types of PDP-amylose aggregates was obtained to allow further analysis. The enthalpy change associated with the guest-host binding equilibrium constant (Kgh) in aqueous solution was estimated to be -75 kJ/mol, which is about twice as high as one might expect based on experimentally measured values of similar complexes in the solid state where the (unsolvated) helical structure of amylose remains rigid. On the other hand, the nonspecific binding (Kns) enthalpy change associated with PDP-amylose interactions in the same solution environment was found to be about half of the inclusion complexation value.

COMPLEX TITANIUM-CONTAINING REAGENTS IN WASTEWATER TREATMENT PROCESSES OF THE FISHING INDUSTRY

The issues of removing nutrients from wastewater from various industries have recently received more and more attention. Traditional coagulants based on aluminum and iron salts can effectively remove phosphate ions from water, but these reagents are not effective against ammonium ions. As part of the work done, the possibility of using complex titanium-containing coagulants in the processes of dephosphatization of wastewater from the fish processing industry was considered. It has been proven that the use of magnesium titanium reagents makes it possible to carry out the coprecipitation of ammonium and phosphate ions in the form of the complex compound of magnesium ammonium phosphate (struvite) with high efficiency. To implement the purification process, a 10–20% stoichiometric excess of magnesium compounds from the calculated value is required, while the efficiency of precipitation of ammonium compounds exceeds 50%, and phosphate anion 95%. The optimal pH range for the process of coprecipitation of ammonium and phosphate ions in the form of a complex compound is 10.0 – 10.5. The results of studies conducted on real water from a fish processing plant demonstrated the increased efficiency of complex titanium-containing reagents compared to traditional coagulants based on aluminum, iron and magnesium salts. The possibility of using magnesium-containing waste from the production of refractory materials has been established both as a precursor for the production of complex coagulants and as an individual reagent. It has been proven that the use of complex titanium-containing reagents makes it possible to significantly intensify the processes of sedimentation (15%) and filtration (20%) of coagulation sludge. The use of complex reagents will significantly increase the level of environmental safety of production and reduce the anthropogenic load on the hydrosphere. For citation: Kuzin E.N. Complex titanium-containing reagents in wastewater treatment processes of the fishing industry. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 127-135. DOI: 10.6060/ivkkt.20246707.6997.

The Physicochemical Basis for the Production of Rapeseed Oil Fatty Acid Esters in a Plug Flow Reactor

This article describes the results of a comprehensive comparative study of the production of fatty acid ethyl esters (FAEEs) for use as biodiesel in perfect mixing reactors (PMRs) and plug flow reactors (PFRs). The products obtained on a laboratory scale at all stages of the separation and purification of the FAEE phase were analyzed using the FTIR, XRF and GC-MS methods. We compared distillation methods for the separation of stoichiometrically excessive ethanol from the reaction mixture. Neutralization methods with H2SO4 solution and carbonation with CO2 were applied for FAEE phase purification from the catalyst. Emulsions formed during the water flushing stage were analyzed via the optical microscopy method. The optimal conditions of stirring speed and temperature were selected to maintain a high level of FAEE–water phase contact area with minimum phase separation time. The efficiency of the carbonation method for catalyst neutralization in the FAEE phase has been proven, allowing us to consider this method as an alternative to the traditional acid neutralization method. According to the results of experimental studies, we have developed a new high-performance technological scheme for the production of fatty acid esters in PFRs. The synthesis of FAEEs in a stoichiometric excess of ethanol of about 1:50 allowed us to increase the reaction rate and productivity of the synthesis unit after the transition from a PMR to a PFR. The yield of the product amounted to 86.7%. The purified FAEE fraction complied with most EN14214 specifications.

Fe-containing sphalerite as a co-catalyst for degradation of Congo red dye

Complex sulfide ores are associated with various sulfide minerals, characterized by their impurity content and physical defects. Sphalerite, a well known Zn-bearing mineral, consists of sulfides and inevitably contains various impurities. In this regard, minor metals in Zn concentrate complicate the flotation process or hydrometallurgical process. Nevertheless, the Fe-containing sphalerite is regarded as an efficient inorganic co-catalyst due to its surface properties with unsaturated S atoms and Fe atoms. Typically, the Fe(III) reduction determines the overall efficiency of the Fenton process, necessitating a stoichiometric excess of H2O2 and catalysts. To address the limitations of the Fenton process, this study proposes the use of Fe-containing sphalerite (ZnS) as co-catalysts to enhance the Fe(III)-H2O2 system. The redox reactions between ZnS and Fe(III) can efficiently decompose H2O2, which promotes the reaction between Fe(III) and Fe(II). Therefore, in this study, ZnS was evaluated as a co-catalyst to enhance the Fenton-like system for the degradation of Congo red (CR). The CR degradation was examined using different processes involving a single factor (ZnS, H2O2), dual factor (ZnS-H2O2, Fe(II)-H2O2, Fe(III)-H2O2), and triple factor (ZnS-Fe(III)-H2O2), to demonstrate co-catalyst effect. It was confirmed that both ZnS and Fe(III) were introduced into the system. Remarkably, 98.9% of ZnS-Fe(III)-H2O2 was degraded within 5 min, underscoring the effectiveness of ZnS as a co-catalyst in enhancing the activating of H2O2. When ZnS-Fe(III)-H2O2 system was used, CR degradation was affected by Fe(III) and H2O2 concentration, ZnS doses, and solution pH. During the reuse experiments, CR could be completely degraded, and Co-catalytic efficiency of ZnS was maintained for three reuse cycles.

Hydrometallurgical recovery of critical metals from an incinerated fly ash of municipal solid waste from western India

ABSTRACT The global generation of 2.2 billion tons of municipal solid waste (MSW) as a result of population growth, rapid urbanization, and industrial development has highlighted an urgent need for MSW management. Incineration is widely accepted as one alternative to landfilling; however, the recovery of heavy metals from the incinerated fly ash (IFA) before its final disposal is highly desirable to make the process sustainable. In this study, we studied the recovery of zinc and lead from typical MSW-IFA employing hydrometallurgical techniques. Sulfuric acid leaching was performed to selectively leach out zinc over the lead at the optimal condition of H2SO4 concentration = 1.5 M, temperature = 30°C, S/L ratio = 150 g/L, time = 2 h, and stirring speed = 300 rpm. The sulfate leach liquor was treated with a 5% stoichiometric excess of oxalic acid to precipitate>99% of zinc to be recovered as ZnC2O4·2 H2O. Further, the remaining lead in leach residue was subsequently leached in 50 g/L NaCl solution for 2 h yielded>94% efficiency. The dissolved lead was crystallized to recover the crystals of PbCl2. The demonstrated process leads towards the recovery of critical metals from an alternative source of MSW-IFA.

Silicon pools, fluxes and the potential benefits of a silicon soil amendment in a nitrogen-enriched tidal marsh restoration

Tidal marshes are important sites of silicon (Si) transformation, where dissolved Si (DSi) taken up by macrophytic vegetation and algal species is converted to biogenic silica (BSi), which can accumulate in the soil, be recycled within the marsh, or be exported to adjacent coastal waters. The role of restored and created tidal marshes in these processes is not well understood, nor is the impact of nutrient enrichment at either the plant or ecosystem level. Here, Si fluxes were examined to develop a Si mass balance in a nitrogen (N)-enriched marsh created with fine-grained dredged material from the Chesapeake Bay, United States. In addition, the effectiveness of Si soil amendments to ameliorate the negative effects of excess nitrogen on Spartina alterniflora was examined through laboratory and field experiments. Silicon was exported to the estuary as DSi (49 g m−2 y−1) and BSi (35 g m−2y−1) in stoichiometric excess of nitrogen and phosphorus. Rapid recycling of Si within both marsh and the tidal creeks appeared to be important in the transformation of Si and export from the marsh. Enhanced macrophyte SiO2 tissue concentrations were observed in the field experiment, with end-of-season mean values of 2.20–2.69% SiO2 in controls and 2.49–3.24% SiO2 in amended plots, among the highest reported for S. alterniflora; however, improved plant fitness was not detected in either experiment. Thus, tidal marshes created with a fine-grained, N-rich dredged material appear to function as a rich source of Si to the restored marsh and local estuarine environment, an overlooked ecosystem service. Soil Si amendments, however, did not appear likely to alleviate N-induced stress in S. alterniflora.

Butyl-esters synthesis from palm fatty acid distillate catalyzed by immobilized lipases in solvent-free system – Optimization using a simplified method (SER)

Palm fatty acid distillate (PFAD) is a residual fatty acids rich-stream obtained in the palm oil refining process. Its potential as raw material for butyl esters syntheses using immobilized lipases (Novozym 435® and Lipozyme RM IM®) in solvent-free system have been explored. A simplified tool for optimizing reaction parameters (Substrate-Enzyme Relation, SER) conciliates the masses of reagents and biocatalysts to obtain valuable insights into the shift of chemical equilibrium and the probability of deleterious effects on immobilized lipases. This mathematical relation had been studied when a single acid and alcohol are involved, but here SER is adopted when a mixture of similar chain-length acids is present in the reaction media. Experimental assays have revealed a range of reaction conditions of molar ratio and biocatalyst loadings equivalent to SER − 42 to − 12, that achieved maximum conversions higher than 90 % using biocatalysts loading lower than 2.0 % (wt/wt of PFAD mass) and less than 10 % of n-butanol stoichiometric excess. Similar SER trends were observed when comparing single reactants conversions results and a mixture of acids (C16–C18) and one alcohol involved, indicating the applicability of SER as optimization tool for enzymatic esterifications using a complex matrix.

Development of a kinetic model of magnetite leaching

The object of the research is the process of magnetite leaching with nitric acid solutions, and the subject of the research is the mathematical justification of the kinetic model and the calculation of kinetic parameters. The article considers the case of leaching in the kinetic region, while magnetite is considered as a polydispersity material of spherical shape. It is proposed to use the distribution function of the number of particles N by their radius r in the form N=a∙rb, where a and b are constants. This distribution was used to derive the equation for the rate of the process W, taking into account the change in the surface of the particles depending on the degree of leaching α: W=dα/dτ=K*∙(1–α)m∙((С0(γ–α)/γ))n, where K* is the rate constant; m and n are the order of solid material and nitric acid, respectively; C0 and γ are the initial concentration of nitric acid and its stoichiometric excess. The order m is defined as m=(b+2)/(b+3), at b→∞ the order m→1. When b=0, m=2/3 is the case of the equation for a shrinking sphere. An algorithm for calculating kinetic parameters in the Excel is proposed. Experimental dependences of the degree of transformation α on time τ are approximated by a third-order equation; by differentiating the obtained equation, the values of the velocity Wexp=dα/dτ at individual points are calculated. After the logarithm of the above equation, there is the expression (γ=1): ln(Wexp)=ln(K*)+m∙ln(1–α)+n∙ln(С0(1–α)). With the help of the «LINEST» function in Excel, for a temperature of 373 K, the values of the order of m=0.93 and n=1.29 and the rate constant K*=0.08 were obtained. Calculation of kinetic parameters for different temperatures takes into account the dependence of the rate constant on temperature: ln(Wexp)=lnk0–E/R∙1/T+m∙ln(1–α)+n∙ln(C0(1–α)). As a result of the calculations, the values n=0.83; m=1.2; E/R=–10402; lnk0=25.09 were obtained. The value of the multiplier k0=exp(lnk0)=7.88∙1010, the activation energy E=–8.31∙E/R=86440 J/mol, the total reaction order n+m=2.03 was calculated. The obtained kinetic parameters were used to determine the calculated values of the rate W. The average relative error between the experimental and calculated values of the leaching rates is 10 %. The proposed method of processing experimental data using a mathematical leaching model can be used for any leaching process.

Rhodium Catalyst Structural Changes during, and Their Impacts on the Kinetics of, CO Oxidation.

Catalysts can undergo structural changes during the reaction, affecting the number and/or the shape of active sites. For example, Rh can undergo interconversion between nanoparticles and single atoms when CO is present in the reaction mixture. Therefore, calculating a turnover frequency in such cases can be challenging as the number of active sites can change depending on the reaction conditions. Here, we use CO oxidation kinetics to track Rh structural changes occurring during the reaction. The apparent activation energy, considering the nanoparticles as the active sites, was constant in different temperature regimes. However, in a stoichiometric excess of O2, there were observed changes in the pre-exponential factor, which we link to changes in the number of active Rh sites. An excess of O2 enhanced CO-induced Rh nanoparticle disintegration into single atoms, affecting catalyst activity. The temperature at which these structural changes occur depend on Rh particle size, with small particle sizes disintegrating at higher temperature, relative to the temperature required to break apart bigger particles. Rh structural changes were also observed during in situ infrared spectroscopic studies. Combining CO oxidation kinetics and spectroscopic studies allowed us to calculate the turnover frequency before and after nanoparticle redispersion into single atoms.

Bifunctional Nanostructured Palladium/MoSx Electrocatalyst for Cathode Hydrogen Evolution Reaction PEM Water Electrolysis and Oxygen Reduction Reaction

AbstractThe creation of effective Pd‐based architectures with numerous electrocatalytic active sites and efficient charge transfer is of key importance for improving the electrocatalytic performance in water electrolyzer and fuel cell applications. On the other hand, MoS2, possessing multiple electrocatalytic active sites, can act both as support and booster to Pd‐based electrocatalytic structures. Herein, MoSx@Pd hybrids were successfully synthesized by using a one‐pot liquid phase solvothermal strategy with stoichiometric excess of Pd. The optimized MoSx@Pd proves to be an excellent bifunctional electrocatalyst for both hydrogen evolution reaction and oxygen reduction reaction (ORR). Optimized MoSx@Pd operates the process for hydrogen evolution at the same potential as Pt/C and achieves a low overpotential of 76 mV at −10 mA cm−2 due to improved reaction kinetics and charge transfer processes between Pd and MoS2. On top of that, MoSx@Pd exhibits excellent performance and stability as cathode electrocatalyst in a polymer electrolyte membrane water electrolyzer. Simultaneously, the bifunctional electrocatalyst shows enhanced electrocatalytic ORR activity and stability by maintaining 93% of its initial activity outperforming commercial Pt/C. Finally, rotating ring disk electrode analysis reveals that ORR proceeds through the energy efficient 4e− pathway, with water being the main product, rendering MoSx@Pd a promising component for fuel cells.

Stoichiometric excesses of H2O2 as dosimetry strategy: proof of concept for UVC-H2O2, dark-Fenton, and UVC-Fenton.

Hydrochlorothiazide (HCT) is a pharmaceuticalmicropollutant highly toxic to the environment, being absolutely necessary to oxidize it completely to CO2. Here, the variables stoichiometric H2O2 excess for (a) degradation and (b) mineralization are defined and used as metric to quantify the dosimetry of the H2O2. So that, dose of H2O2 qualifies being under- and over-dose respectively for values below and above such standards. In this work, these concepts have been elucidated across AOPs regarding the H2O2 degradation excess, whereas only UVC-Fenton was used regarding the H2O2 mineralization excess. At a H2O2 mineralization excess of 0.68 (equivalent to degradation excess of 36.74), oxidation via UVC-H2O2 enables absolute (100%) HCT degradation within 60min; however, the mineralization of HCT demonstrated limited optimization for all AOPs employed in the beaker-like reactor of this work, being the underlying reasons investigated hereby. At best, 26.70% HCT mineralization was observed within 60min of UVC photo-Fenton using an initial 2.00 H2O2 mineralization excess. Such mineralization of 26.7% is unexpectedly low considering that, in addition, the residual H2O2 concentration almost fully depletes within 30min of UVC-Fenton oxidation. Taken all that together, the loss of H2O2 due its decomposition induced by the risen temperature from 28 to 70ºC very likely were the underlying reason preventing better mineralization performance. We successfully demonstrated 18% of mean efficiency of radical •OH consumption signals that the overheating is indeed a designer problem with the photo-reactor since a well-refrigerated photo-reactor shows a mean efficiency of 38% for the same H2O2 excess.

Efficiency of the H2O2 consumption by the mineralization of hydrochlorothiazide via photo-Fenton UVA: a time dependent analysis

In the photochemical conversion of hydrogen peroxide (H2O2) into radical ·OH, the rule of radiation dose (the quantum yield) on the oxidation kinetics is well known. In contrast, the H2O2 dose mostly remains an attempt-and-error variable. Here, we propose a method to estimate the efficiency of H2O2 dose consumption by the mineralization micro-kinetics that enables a generalist strategy for a more cost-effective dose of the oxidant. It needs the time-dependent H2O2, micropollutant, and product (CO2) measure. Photo-Fenton (FP) hydrochlorothiazide (HCT) oxidation using a tubular photo-reactor and UVA radiation assisted in demonstrating the method. The average value of ~ 38% was on top of the best efficiencies associated with some of the fastest mineralization rates. Such efficiencies depend on the stochiometric concentration of the oxidant. Here, the variable stoichiometric H2O2 excess for mineralization is proposed as a universal metric to quantify the (under-) over-dose of H2O2. Overall, H2O2 excess between 2 and 5 leads to H2O2 consumption efficiencies above 30%, together with a fast rate of CO2 formation (mineralization). In contrast, any value below one invariably leads to a sluggish oxidation rate, leading even to the total depletion of the oxidant. Besides proposing a selection criterion for the most cost-effective H2O2-dose and providing some examples, this work carefully analyzes the commitment of the H2O2 excess concerning the energy costs (EEO).

SmiA is a hybrid priming/scaffolding adaptor for the LonA protease in Bacillus subtilis

Regulatory proteolysis targets properly folded clients via a combination of cis-encoded degron sequences and trans-expressed specificity factors called adaptors. SmiA of Bacillus subtilis was identified as the first adaptor protein for the Lon family of proteases, but the mechanism of SmiA-dependent proteolysis is unknown. Here, we develop a fluorescence-based assay to measure the kinetics of SmiA-dependent degradation of its client SwrA and show that SmiA–SwrA interaction and the SwrA degron were both necessary, but not sufficient, for proteolysis. Consistent with a scaffolding adaptor mechanism, we found that stoichiometric excess of SmiA caused substrate-independent inhibition of LonA-dependent turnover. Furthermore, SmiA was strictly required even when SwrA levels were high suggesting that a local increase in substrate concentration mediated by the scaffold was not sufficient for proteolysis. Moreover, SmiA function could not be substituted by thermal denaturation of the substrate, consistent with a priming adaptor mechanism. Taken together, we conclude that SmiA functions via a mechanism that is a hybrid between scaffolding and priming models.

Filament dynamics in vertical confined chemical gardens.

When confined to a Hele-Shaw cell, chemical gardens can grow as filaments, narrow structures with an erratic and tortuous trajectory. In this work, the methodology applied to studies with horizontal Hele-Shaw cells is adapted to a vertical configuration, thus introducing the effect of buoyancy into the system. The motion of a single filament tip is modeled by taking into account its internal pressure and the variation of the concentration of precipitate that constitutes the chemical garden membrane. While the model shows good agreement with the results, it also suggests that the concentration of the host solution of sodium silicate also plays a role in the growth of the structures despite being in stoichiometric excess.

Biogeochemical functioning of the Baltic Sea

Abstract. Location, specific topography, and hydrographic setting together with climate change and strong anthropogenic pressure are the main factors shaping the biogeochemical functioning and thus also the ecological status of the Baltic Sea. The recent decades have brought significant changes in the Baltic Sea. First, the rising nutrient loads from land in the second half of the 20th century led to eutrophication and spreading of hypoxic and anoxic areas, for which permanent stratification of the water column and limited ventilation of deep-water layers made favourable conditions. Since the 1980s the nutrient loads to the Baltic Sea have been continuously decreasing. This, however, has so far not resulted in significant improvements in oxygen availability in the deep regions, which has revealed a slow response time of the system to the reduction of the land-derived nutrient loads. Responsible for that is the low burial efficiency of phosphorus at anoxic conditions and its remobilization from sediments when conditions change from oxic to anoxic. This results in a stoichiometric excess of phosphorus available for organic-matter production, which promotes the growth of N2-fixing cyanobacteria and in turn supports eutrophication. This assessment reviews the available and published knowledge on the biogeochemical functioning of the Baltic Sea. In its content, the paper covers the aspects related to changes in carbon, nitrogen, and phosphorus (C, N, and P) external loads, their transformations in the coastal zone, changes in organic-matter production (eutrophication) and remineralization (oxygen availability), and the role of sediments in burial and turnover of C, N, and P. In addition to that, this paper focuses also on changes in the marine CO2 system, the structure and functioning of the microbial community, and the role of contaminants for biogeochemical processes. This comprehensive assessment allowed also for identifying knowledge gaps and future research needs in the field of marine biogeochemistry in the Baltic Sea.

Cuprizone-induced Demyelination in Mouse Brain is not due to Depletion of Copper.

The cuprizone (CPZ) model allows the study of the biochemical processes underlying nonautoimmune-mediated demyelination, remyelination, and chronic white matter disease progression. CPZ is a copper (Cu) chelator that chiefly causes oligodendrocyte apoptosis in the corpus callosum and cerebellum when administered in the mouse diet. While disruption of Cu homeostasis is known to cause neurodegeneration (as is observed in Wilson’s and Menkes disease), no consensus exists to date as to CPZ’s mechanism of action. We sought to determine whether CPZ-induced pathology is due to Cu depletion as is generally believed. Cu supplementation in chow, in stoichiometric excess to the added CPZ, did not reduce CPZ-induced demyelination in C57Bl/6 mice. Moreover, equivalent doses of other known Cu chelators neocuproine and D-penicillamine (D-Pen) failed to induce central nervous system (CNS) demyelination. Since administration of D-Pen in the treatment of Wilson’s disease can induce hypocupremia, we next sought to recreate penicillamine-induced Cu deficiency to compare with purported CPZ-induced Cu deficiency. The resulting clinical phenotype and histopathology were unlike that of CPZ. D-Pen-treated mice exhibited digit paralysis, tail flaccidity, subcutaneous hemorrhaging, and optic and sciatic neuropathy, all of which were prevented with Cu supplementation. No demyelination of the corpus callosum or cerebellum was observed, even with D-Pen doses tenfold higher than CPZ. Intriguingly, addition of D-Pen to the CPZ diet paradoxically prevented demyelination in a dose-dependent manner.Summary StatementThe demyelinating effects of CPZ are not due to Cu deficiency but are instead consistent with acute toxicity of a CPZ + Cu complex.

Optimized conditions for reduction of iron (III) oxide into metallic form under hydrogen atmosphere: A thermodynamic approach

Incomplete reduction of Fe2O3(s) iron oxide into metallic Fe(s), under hydrogen, is a challenge for iron-based catalysts limiting their industrialization for methane reforming or decomposition. This work provides thermodynamic models generated using the HSC 7.1 Chemistry software, based on minimization of total Gibbs free energy and provides amount of species resulting from the reduction of iron oxide under hydrogen. Molar ratios of Fe2O3 to H2(g) were varied from stoichiometric till hydrogen excess. An optimum molar ratio for highest reduction degree of iron oxides into metal was defined. Results show that direct reduction of Fe2O3(s) into Fe(s) is not possible, but a series of H2-induced reduction steps along with other side-reactions take place yielding, partially reduced iron oxides species. An optimized Fe2O3:H2 molar ratio exceeding 0.25:3 is needed to favor reduction of FeO(s) into Fe(s)0. For validation, simulated values were compared with experimental ones from literature (reduced amounts of iron oxide).

Solvent‐Free Glycosylation from per‐O‐Acylated Donors Catalyzed by Methanesulfonic Acid

AbstractThe huge importance of carbohydrates and their derivatives in biomedical and industrial applications call for the development of streamlined and sustainable procedures for their synthetic elaboration. Here reported a novel glycosylation method based on direct activation of readily available per‐O‐acylated (acetylated or benzoylated) donors, promoted under air by methanesulfonic acid as a cheap and green catalyst in the absence of any solvent. Besides the beneficial avoidance of toxic and polluting organic solvents, these conditions were found critical for activating such poorly reactive donors with a very small catalyst loading (only 5 mol %), instead of stoichiometric Lewis acid promoters typically employed. Desired glycosides were quickly obtained, in most cases with high 1,2‐transstereoselectivity. Other main advantages over reported glycosylations with similar donors are the limited stoichiometric excess of the acceptor (or the donor), the easy applicability and low cost of the procedure and the wide target scope, also covering the synthesis of disaccharides and other non‐trivial glycosides with applicable potential.