MeOH Concentration Research Articles

Spectroscopic insights into BSA-mediated deaggregation of m-THPC

Meta-tetra(hydroxyphenyl)chlorin (m-THPC) is among the most potent photosensitizers, known for its high singlet oxygen generation efficiency. However, its clinical effectiveness in photodynamic therapy (PDT) is compromised by its propensity to aggregate in aqueous solutions, adversely affecting its photophysical properties and therapeutic potential. A series of spectroscopic techniques, including UV-Vis absorption, fluorescence spectroscopy, and laser flash photolysis, revealed that m-THPC exhibits significant aggregation, particularly in MeOH-PBS mixtures with MeOH content below 30%. This aggregation adversely affects its photophysical properties leading to reduced fluorescence quantum yield and most importantly reducing its singlet oxygen quantum yield. This study introduces the use of bovine serum albumin (BSA) to counteract the aggregation of m-THPC, aiming to enhance its solubility, stability, and efficacy in physiological settings. Through advanced spectroscopic analyses we demonstrated that the m-THPC@BSA complex exhibits restored photophysical properties characteristic for monomeric form. Notably, the complex showed a significant restoration of the singlet oxygen quantum yield (ΦΔ = 0.21) compared to aggregated m-THPC. These results underscore the potential of BSA to preserve the monomeric form of m-THPC, mitigating aggregation-induced losses in singlet oxygen production. Our findings suggest that BSA-mediated delivery systems could play a crucial role in optimizing the clinical utility of hydrophobic photosensitizers like m-THPC.

Para-Hydroxy Ni(II)-POCOP Pincer Complexes as Modifiers on Carbon Paste Electrodes and Their Application in Methanol Electro-Oxidation in Alkaline Media

The application of organometallic materials as anodes in fuel cell devices has experienced a notable increase in recent years. However, the use of POCOP pincer complexes remains scarcely explored despite their great relevance in catalysis. Thus, in this work, the electrocatalytic activity to methanol in alkaline media of three Ni(II)-based POCOP pincer complexes—[NiCl{C6H2-4-OH-2,6-(OPiPr2)2}] (a1), [NiCl{C6H2-4-OH-2,6-(OPtBu2)2}] (a2), and [NiCl{C6H2-4-OH-2,6-(OPPh2)2}] (a3)—will be discussed. The complexes were use as modifiers of carbon paste electrodes that were evaluated using cyclic voltammetry considering diverse factors, such as the absence and presence of MeOH, diverse proportions (% w/w) of the complex in the electrode, scan rate, and different MeOH concentrations. Results indicated the presence of a redox pair Ni(II)/Ni(III) with a quasi-reversible behavior in all complexes, the anodic peak currents of which were proportional to the increase in MeOH concentrations (0.05–0.3 mM), and their oxidation potentials varied in the function of the P-substituent in the Ni(II)-POCOPs backbone. Complex a1 exhibited the best current density (429.5 mA cm2 at 0.5 mM) compared to its analogs a2 and a3. The current intensity of all electrodes displays good stability, which remains—with slight changes—up to 100 s. Moreover, a comparison of their catalytic rate constants suggested a great activity in complex a1 (0.52 × 106 cm3 mol−1 s−1) compared to its analogues, implying a great activity in the electro-oxidation of MeOH. Hence, this work opens new opportunities for the electrochemical application of POCOPs complexes for future DMFCs development.

Valorisation of organic carbons and organo-solvents by mixotrophic cultivation of methylotrophic Tetraselmis indica for enhanced biomolecules production

Microalgal biomass is a sustainable bioresource for producing a wide range of biomolecules such as lipids and chlorophylls, astaxanthin, and β-carotene. The mixotrophic cultivation using organic carbon (OCs) and traditional organo-solvents (OSs), especially methanol (MeOH), has been shown to improve biomass productivity and biomolecule yield. However, limited studies have explored the utilization of OSs as an external carbon source to produce microalgal biomass and for subsequent biorefinery. Thus, the present study evaluates the effects on the cultivation of industrial important microalgal Tetraselmis indica BDUG001 (T. indica BDUG001) through supplementation of various OCs and OSs at different day-night cycles under sterile mixotrophic conditions. Among all the OCs and OSs, MeOH showed the best growth, biomass, and biomolecule production. Interestingly, MeOH at a varying concentration (0–10 g/L) was an ideal carbon source for enhancing T. indica BDUG001 growth, biomass, and biomolecules productivity. At the 7.5 g/L concentration of MeOH, T. indica BDUG001 showed maximized biomass production (2.45 ± 0.07 g/L), lipid content (42.85 ± 1.20%), total lipid yield (1.05 ± 0.03 g/L), photosynthetic pigments [chl-a (3.27 mg/L), chl-b (2.25 mg/L) and TCs (1.27 mg/L]. While the maximum astaxanthin (0.77 μg/gm) and β-carotene (5.21 μg/mg) were observed at 10 and 5.0 g/L, respectively. The present investigation will aid in the microalgal research pipeline for the selection of novel OSs tolerant microalgae strains and utilization of waste OSs for mass-scale sterile mixotrophic cultivation. Moreover, the proposed cultivation system will help to develop low-cost algal biorefinery systems to attain high-quality industrial important biomolecules.

Solvent-Directed Hierarchical Self-Assembly of Tetraphenylpyrazine-Cholesterol with Amplified Circularly Polarized Luminescence.

It is important to identify the effect of assembly and aggregation on the chirality transfer and energy transmission in supramolecular polymer system, since the unordered aggregation is insufficient to promote luminescence enhancement and chirality transfer, even causing the negative effect. Another key issue is to identify the solvent effect on hierarchically chiral self-assembly. Herein, we designed an AIE-core based building block, tetraphenylpyrazine-cholesterol (TPP-Chol), to explore how the solvent component influences chirality transfer and energy transmission of its aggregates and/or assemblies. Interestingly, the hierarchical assembly behavior was realized in the mixture of MeOH/CHCl3 highly dependent on the MeOH content. During the solvent-directed hierarchical assembly, the morphologic transformations, such as nanoribbons with a width of 150 nm, twisted nanoribbons with helical pitch of 420 nm, nanoribbon clusters, and microflowers with an average diameter of 5.5 μm, were realized with obvious chirality amplification for both circular dichroism (CD) and circularly polarized luminescence (CPL) measurements. The hierarchical assembly of TPP-Chol was also demonstrated by a time-dependent CD test. The work points out the complexity and dynamic of hierarchically chiral self-assembly regulated by the solvent effect, which would be helpful for the development of supramolecular materials with enhanced CPL performance and dynamic chirality.

Efficient Recovery Strategy of Luteolin from Agricultural Waste Peanut Shells and Activity Evaluation of Its Functional Biomolecules.

Peanut shells (PSs) generated from agricultural waste contain valuable compounds with bioactive properties such as anti-aging, antimicrobial, and antioxidant properties, making it desirable to recycle them as a sustainable resource. The aim of this study is to design an effective luteolin recovery process as the first step of an integrated biorefinery utilizing PSs as raw material. The major extraction variables and their ranges for luteolin recovery from PSs were determined (0-60 °C, 1-5 h, 0-100% MeOH concentration) and a predictive model was derived through a response surface methodology (RSM). Based on the predictive model, the equation determined for the maximal extraction of luteolin at 1 h was as follows: y = -1.8475x + 159.57, and the significant range of variables was as follows: 33.8 °C ≤ temperature (x) ≤ 48.5 °C and 70.0% ≤ MeOH concentration (y) ≤ 97.5%, respectively. High antioxidant and elastase inhibitory activities of PS extracts were confirmed, and these results support their potential to be used as functional materials. In addition, 39.2% of the solid residue after extraction was carbohydrate, which has potential as a carbon source for fermentation. This study provides a useful direction on an integrated biorefinery approach for sustainable agricultural waste valorization.

Metal–organic framework mediated Ni-deposition on MWCNTs for direct methanol fuel cell catalysis

Herein, we present the utilization of Ni2+-doped, amine-functionalized, UiO-66-NH2 metal–organic framework (MOF) nanoparticles deposited onto multi-walled carbon nanotubes (MWCNTs) as a precursor to generate electrocatalytically active catalyst towards methanol (MeOH) oxidation. The electrode material displayed an onset potential of 0.42 V (vs Hg/HgO) with maximum activity at 1 M MeOH concentration (143 mA/cm2 current density at 0.6 V vs Hg/HgO). The catalyst also demonstrated high stability, retaining 93.5% of its initial activity under continuous electrolysis for 1 h, and 84.1% after 10 h.

Characterization of Antioxidant and α-Glucosidase Inhibitory Compounds of Cratoxylum formosum ssp. pruniflorum and Optimization of Extraction Condition.

Cratoxylum formosum ssp. pruniflorum (Kurz.) Gogel (Guttiferae), called kuding tea, is widely distributed in Southeast Asia. In this study, the constituents and biological activity of C. formosum ssp. pruniflorum were investigated. Extract of its leaves, roots and stems showed antioxidant and α-glucosidase inhibitory activity. Interestingly, comparison of the metabolite profiles of leaves, roots and stems of C. formosum ssp. pruniflorum by LC-MS analysis showed a great difference between the roots and leaves, whereas the roots and stems were quite similar. Purification of the roots and leaves of C. formosum ssp. pruniflorum through various chromatographic techniques resulted in the isolation of 25 compounds. The structures of isolated compounds were elucidated on the basis of spectroscopic analysis as 18 xanthones, 5 flavonoids, a benzophenone and a phenolic compound. Among them, a xanthone (16) and a benzophenone (19) were first reported from nature. Evaluation of biological activity revealed that xanthones had a potent α-glucosidase inhibitory activity, while flavonoids were responsible for the antioxidant activity. To maximize the biological activity, yield and total phenolic content of C. formosum ssp. pruniflorum, extraction conditions such as extraction solvent, time and temperature were optimized using response surface methodology with Box-Behnken Design (BBD). Regression analysis showed a good fit of the experimental data, and the optimal condition was obtained as MeOH concentration in EtOAc, 88.1%; extraction time, 6.02 h; and extraction temperature 60.0 °C. α-Glucosidase inhibitory activity, yield and total phenolic content under the optimal condition were found to be 72.2% inhibition, 10.3% and 163.9 mg GAE/g extract, respectively. These results provide useful information about C. formosum ssp. pruniflorum as functional foods for oxidative stress-related metabolic diseases.

Preparation of High-quality Oil from Vegetable Oil with High-free Fatty Acid (FFA) Content Using an Ammonia/Methanol Solution.

There are significant concerns regarding the quality of vegetable oils in the food and biofuel industries. In this study, we explored the preparation of high- quality oil from high-free fatty acid (FFA) vegetable oil using an ammonia/MeOH solvent as an alkali base. Among the six tested solvents, MeOH was the most suitable for the separation of the oil and FFAs. Among the three alkali bases, ammonia enhanced the miscibility of FFAs in MeOH by forming ammonium salts. The amounts of FFAs in the upper layer and oil in the lower layer were positively correlated (r = 0.9348 and 0.9617, respectively) with MeOH. With increasing MeOH concentration, the amount of oil in the lower layer increased along with the FFAs in the upper layer. Using the molar ratio of ammonia to FFA 1:1 and the ratio (v/w) of MeOH to oil 4:3, 91.6% FFAs and 97.8% oil in the upper and lower layers, respectively, were produced from 50% FFA oil. Using a relational expression of FFAs and oil in the upper layer, 97.1% FFAs and 99.6% oil in each layer was obtained from 10% FFA oil. The oil in the lower layer was further purified by extraction with MeOH. This method is easy and efficient for the separation and purification of oil, accompanied by the reuse of reagents with almost no loss of raw materials.

(Digital Presentation) Electrocatalytic Oxidation of Methanol over Silver Based Electrocatalysts Synthesized By Solution Combustion Technique

Herein, we report the electrocatalytic properties of Ag-M/C (M=Cu, Zn, Fe, Cr, Mn) catalysts produced using solution combustion synthesis (SCS) method for methanol oxidation reaction (MOR). The morphological properties of the synthesized catalysts were studied using SEM, EDX, TEM, XRD and XPS techniques. The characterization results indicated that out of all catalysts, AgCu/C had the most porous surface, small and well distributed particles with high surface area making it a good choice for electrocatalytic experiments. The XPS results showed a shift in peak in the AgCu/C sample due to the charge transfer between Ag and Cu indicating a strong interaction between Ag and Cu. The electrochemical properties of the catalysts were studied at 1 M methanol concentration and 1 M KOH (electrolyte) concentration by performing Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) experiments. It was observed that AgCu/C exhibited a greater electrocatalytic activity and was therefore, found to be a more viable catalyst for MOR. Following this, further concentration studies were conducted on AgCu/C for methanol concentrations of 0.5M, 1M, 1.5M, 2.5M to evaluate the rate dependency of the catalyst on MeOH concentration. The CV and LSV curves depicted a linear increase in current density proportional to the increase in methanol concentration, indicating power-law dependency. The catalyst also displayed long-term stability when chronoamperometry test was performed for 20 hours.

Screening of Low-Dosage Methanol as a Hydrate Promoter

We report a quantitative study of the effect of low-concentration methanol (MeOH) on the formation and dissociation of hydrates based on CH4 and CO2/N2 guest molecules. The kinetic promotion and dissociation ability of MeOH is also compared with the anionic surfactant sodium dodecyl sulfate (SDS, 100 ppm, 50 ppm). The effects of concentration changes (1 wt% and 5 wt%), pressure (p = 80–120 bar), guest molecules (CH4 and CO2), and temperature (1 °C and below 0 °C) are investigated using slow constant ramp (SCR) and isothermal (IT) temperature schemes. The results show that the kinetics are affected by the guest molecule and MeOH concentration. For CH4 gas, 5 wt% MeOH shows better promotion, while for CO2/N2 gas mixtures, 1 wt% MeOH gives better promotion. This conclusion agrees well with our previous results demonstrating optimal CH4 recovery and CO2 storage in the presence of 5 wt% MeOH. The promoting and inhibiting properties of MeOH could be beneficial in CH4 production from gas hydrate using CO2-rich gas injection, as delayed hydrate film formation in the presence of MeOH could improve both CH4 recovery and CO2 storage.

A Novel Methanol-Based DP Estimation Method With a New Methanol Peak Detector Index for Aging Assessment of Power Transformer Insulation Paper

Methanol concentration as an aging indicator can assess cellulose aging and estimate cellulose degree of polymerization (DP). Despite the advantages of methanol (MeOH), its major disadvantage is that its concentration in the oil decreases after some time. This point is called the MeOH peak in this article. Therefore, using this indicator when MeOH concentration is reduced leads to incorrect results. When using methanol, the main problem is that whenever the methanol concentration in a transformer is measured, it cannot be identified that the measured concentration belongs to the left or right side of the MeOH peak. If the measured concentration belongs to the right side of the MeOH peak, the estimated DP is incorrect. In this article, an empirical equation is established to estimate the DP value as a function of methanol concentration when methanol concentration belongs to the left side of the MeOH peak. Then, a new index called methanol peak detector index (MPDI) composed of a 2-furfural/MeOH ratio and normalized DP is presented to ensure the validity of the calculated DP value. If it is found that the measured concentration belongs to the left side of the MeOH peak, then the estimated DP by the presented equation is valid. Finally, the application of this method is verified by applying it to measurement data samples indicating the validity of the method.

Methanol concentration as a preceding eliminative marker for the authentication of Scotch Whiskies in Taiwan

Modern rectified spirit is distilled ethanol (EtOH) containing only a tiny amount of methanol (MeOH), as opposed to former industrial alcohol, and is frequently used by perpetrators to adulterate or counterfeit Scotch whiskies in Taiwan. As a result, MeOH level presents an obvious discrepancy between adulterated whiskies and authentic Scotch whiskies. In this study, 54 authentic single malt Scotch whisky samples and 30 authentic blended Scotch whisky samples were comparatively analyzed. Instead of various analog internal standards often spiked for GC/MS quantitative analyses, the isotope-labeled internal standard 2H3-MeOH was employed for optimizing the Scotch whisky analysis to achieve a limit of quantitation (LOQ) of 5 ppm for MeOH. The resulting data were further analyzed by a distribution fitting method and showed that the distribution of MeOH levels corresponded to a lognormal distribution for both authentic single malt Scotch whiskies and authentic blended Scotch whiskies. Based on the statistical characteristics of the lognormal distribution, 99.7% of the MeOH concentrations would lie between 13.4 and 44.2 ppm for authentic single malt Scotch whiskies and between 7.87 and 74.9 ppm for authentic blended Scotch whiskies, suggesting that the MeOH level might serve as a marker for the authentication of the seized Scotch whiskies in Taiwan.

Methanol Electro-Oxidation over Combustion Synthesized Silver Based Electrocatalysts

Herein, we report the electrocatalytic properties of Ag-M/C (M=Cu, Zn, Fe, Cr, Mn) catalysts produced using solution combustion synthesis (SCS) method for methanol oxidation reaction (MOR). The morphological properties of the synthesized catalysts were studied using SEM, EDX, TEM, XRD and XPS techniques. The characterization results indicated that out of all catalysts, AgCu/C had the most porous surface, small and well distributed particles with high surface area making it a good choice for electrocatalytic experiments. The XPS results showed a shift in peak in the AgCu/C sample due to the charge transfer between Ag and Cu indicating a strong interaction between Ag and Cu. The electrochemical properties of the catalysts were studied at 1 M methanol concentration and 1 M KOH (electrolyte) concentration by performing Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) experiments. It was observed that AgCu/C exhibited a greater electrocatalytic activity and was therefore, found to be a more viable catalyst for MOR. Following this, further concentration studies were conducted on AgCu/C for methanol concentrations of 0.5M, 1M, 1.5M, 2.5M to evaluate the rate dependency of the catalyst on MeOH concentration. The CV and LSV curves depicted a linear increase in current density proportional to the increase in methanol concentration, indicating power-law dependency. The catalyst also displayed long-term stability when chronoamperometry test was performed for 20 hours.

Macrocyclic glycopeptides- and derivatized cyclofructan-based chiral stationary phases for the enantioseparation of fluorinated ß-phenylalanine analogs

The enantioseparation of five fluorinated β-phenylalanine analogs together with the nonfluorinated α- and β-phenylalanines has been investigated utilizing chiral stationary phases. The employed chiral selectors include macrocyclic antibiotics, such as vancomycin, teicoplanin, and teicoplanin aglycone, isopropyl carbamate functionalized cyclofructan-6, and Cinchona alkaloid-based tert.-butyl carbamate quinine, all covalently bonded to 2.7 µm superficially porous silica particles. The applied conditions included reversed-phase and polar-ionic modes where the vancomycin-, and the cyclofructan-6-based core-shell particles proved to offer suitable efficiency. Under reversed-phase conditions typical hydrophobic chromatographic behavior was observed, especially in the H2O/MeOH system. The improved selectivity with increasing MeOH content observed in polar ionic mode suggests that H-bonding may not play a major role in the chiral recognition. The stoichiometric displacement model was probed to gather information on the ionic interactions. The ion-exchange process was found to affect retention, but it has no essential contribution to chiral recognition. Without paying special attention to the optimization of the system volume of the UHPLC instrument plate heights varying in the range of 10–50 µm were obtained. In all cases, retention and selectivity decreased with increasing temperature, and enthalpy-driven enantiorecognition was observed. Elution sequences were determined in all cases.

Recycling reaction and separation for FACylation of loxenatide by trade-off between miscibility and immiscibility of reactants and product in methanol solution

The growing demand and scale of production for fatty acid chain modified (FACylated) polypeptide has sparked the interest in novel production technologies. In this study, a recycling reaction and separation process was proposed and applied to the fatty acid chain modification (FACylation) of loxenatide (LOX), which was based on the difference in solubility between reactants and FACylated product. Especially, the mixed PBS-Methanol (MeOH) solution was designed to meet the demands for FACylation of LOX as well as separation of FACylated LOX and residual modifier. In order to ensure the efficient FACylation, a mixed 10% PBS-90% MeOH (v/v) solution was chosen to provide a good miscibility for two reactants, LOX and N-tetradecylmaleimide (C14-MAL). On the other hand, the immiscibility between reactant (C14-MAL) and FACylated product (N-tetradecyl-Loxenatide (C14-LOX)) could realize the separation of C14-LOX when the MeOH concentration was less than 30% (v/v). Based on this strategy, the recycling reaction and separation process for FACylation of LOX was established by adjusting the MeOH concentration in the mixed solution. The reaction yield and recovery of C14-LOX exceeded 97% and 94%, and the excess reactant C14-MAL could be recycled with a recovery of more than 80%. Furthermore, after purification by reversed-phase chromatography, C14-LOX showed good pharmacokinetic and pharmacodynamic properties in vivo. This study will have great application prospects in industrial production of C14-LOX.

Standard-Free Quantification of Dicarboxylic Acids: Case Studies with Salt-Rich Effluents and Serum.

The present study evaluates the ionization efficiency (IE) of linear and branched C2-C14 dicarboxylic acids (DCAs) by electrospray ionization (ESI) under different conditions. The influence of the concentration of organic modifier (MeOH); mobile phase additive; and its concentration, pH, and DCA structure on IE values is studied using flow injection analysis. The IE values of DCAs increase with the increase of MeOH concentration but also decrease with an increase of pH. The former is due to the increase in solvent evaporation rates; the latter is caused by an ion-pairing between the diacid and the cation (ammonium), which is confirmed by the study with different amines. The investigation of DCA ionization in the presence of different acidic mobile phase additives showed that a significant improvement in the (-)ESI responses of analytes was achieved in the presence of weak hydrophobic carboxylic acids, such as butyric or propanoic acid. Conversely, the use of strong carboxylic acids, such as trichloroacetic acid, was found to cause signal suppression. The results of the IE studies were used to develop the liquid chromatography-high-resolution mass spectrometry (LC-HRMS) method that provided instrumental limits of detection in the range from 6 to 180 pg. Furthermore, upon applying the nonparametric Gaussian process, a model for the prediction of IE values was developed, which contains the number of carbons in the molecule and MeOH concentration as model parameters. As a case study, dicarboxylic acids are quantified in salt-rich effluent and blood serum samples using the developed LC-HRMS method.

Effects of Electrolytes on the Dediazoniation of Aryldiazonium Ions in Acidic MeOH/H2O Mixtures

Aryldiazonium, ArN2+, ions decompose spontaneously through the formation of highly reactive aryl cations that undergo preferential solvation by water, showing a low selectivity towards the nucleophiles present in their solvation shell. In this work, we investigate the effects of electrolytes (NaCl, LiCl, and LiClO4) on the dediazoniation of 2-, 3-, and 4-methylbenzenediazonium ions in acidic MeOH/H2O mixtures. In the absence of electrolytes, the rates of dediazoniation, kobs, increase modestly upon increasing the MeOH content of the reaction mixture. At any solvent composition, the rate of ArN2+ loss is the same as that for product formation. The main dediazoniation products are cresols (ArOH) and methyl phenyl ethers (ArOMe). Only small amounts (less than 5%) of the reduction product toluene (ArH), which are detected at high percentages of MeOH. Quantitative yields of are obtained at any solvent composition. The addition of LiCl or NaCl ([MCl] = 0–1.5 M) to the reaction mixtures has a negligible effect on kobs but leads to the formation, in low yields (<10%), of the ArCl derivative. The addition of LiClO4 (0–1.5 M) to 20% MeOH/H2O mixtures has a negligible effect on both kobs and on the product distribution. However, at 99.5% MeOH, the addition of the same amounts of LiClO4 leads to a modest decrease in kobs but to a significant decrease in the yields of ArOMe. Results are interpreted in terms of the preferential solvation of perchlorate ions by the aryl cations, removing MeOH molecules from the solvation shell.

Deep Decarbonization of the Cement Sector: A Prospective Environmental Assessment of CO2 Recycling to Methanol

Current decarbonization pressures are prompting efforts to reimagine the future of the hard-to-abate cement sector. To date, fuel switching has arisen as the most readily operational strategy, and its application in the cement sector is expected in the short to midterm. However, around two-thirds of the cement CO2 emissions come from the calcination of limestone. The implementation of CO2 capture utilization and/or storage will be crucial to support a reliable net-zero carbon future by 2050–2070. CCS is considered as the most carbon-neutral technology in the cement decarbonization roadmap, while CO2 recycling (CCU) has arisen as a suitable strategy for those locations where there is an industrial symbiosis between the cement market and CO2-based chemical markets (e.g., methanol, formic acid, etc.). Despite that the CCU strategy cannot be carbon-neutral by itself, it could be a powerful option in combination with CCS. To date, most CO2 recycling technologies are still emerging, and their development has to be boosted in the next decades. In this study, a prospective environmental analysis has been conducted through life cycle thinking to explore the benefits of cement long-term decarbonization by implementing a carbon recycling plant (CRP) based on the emerging electrochemical reduction (ER) of CO2 to produce methanol (MeOH). The study aims to demonstrate the synergic decarbonization and defossilization for both cement and MeOH markets, respectively. Cell energy efficiency and MeOH concentration have been identified as the key performance parameters that should be around 60% and 40% wt, respectively, to ensure a future sustainable implementation of ER to the MeOH technology. A CRP powered by low-carbon renewable electricity (<0.02 kg CO2eq/kW h) and with a low-fossil depletion (FD) impact (<0.01 kg oileq/kW h) could lead to an integrated cement and MeOH production with sharp reductions in the carbon footprint (∼75%) and FD (∼66%) of the integrated cement and MeOH production compared to the conventional fossil-based productions. The proposed CO2 recycling scheme can contribute to accelerating the innovation of carbon capture and recycling technologies and their deployment in these hard-to-abate sectors.

Biochemical Methanol Gas Sensor (MeOH Bio-Sniffer) for Non-Invasive Assessment of Intestinal Flora from Breath Methanol

Methanol (MeOH) in exhaled breath has potential for non-invasive assessment of intestinal flora. In this study, we have developed a biochemical gas sensor (bio-sniffer) for MeOH in the gas phase using fluorometry and a cascade reaction with two enzymes, alcohol oxidase (AOD) and formaldehyde dehydrogenase (FALDH). In the cascade reaction, oxidation of MeOH was initially catalyzed by AOD to produce formaldehyde, and then this formaldehyde was successively oxidized via FALDH catalysis together with reduction of oxidized form of β-nicotinamide adenine dinucleotide (NAD+). As a result of the cascade reaction, reduced form of NAD (NADH) was produced, and MeOH vapor was measured by detecting autofluorescence of NADH. In the development of the MeOH bio-sniffer, three conditions were optimized: selecting a suitable FALDH for better discrimination of MeOH from ethanol in the cascade reaction; buffer pH that maximizes the cascade reaction; and materials and methods to prevent leaking of NAD+ solution from an AOD-FALDH membrane. The dynamic range of the constructed MeOH bio-sniffer was 0.32–20 ppm, which encompassed the MeOH concentration in exhaled breath of healthy people. The measurement of exhaled breath of a healthy subject showed a similar sensorgram to the standard MeOH vapor. These results suggest that the MeOH bio-sniffer exploiting the cascade reaction will become a powerful tool for the non-invasive intestinal flora testing.

A unified thermodynamic framework to compute the hydrate formation conditions of acidic gas/water/alcohol/electrolyte mixtures up to 186.2 MPa

The coexistence of acid gas/water/alcohol/electrolyte mixtures is common during the gas production process. Traditional methods have difficulty accurately predicting hydrate formation temperatures and pressures because of complicated molecular and ionic interactions in such mixture components. Based on the electrolyte Cubic-Plus-Association (e-CPA) equation of state (EoS) and the Parrish-Prausnitz model, this paper proposed a unified thermodynamic model to describe the multiple interactions of acid gas/water/alcohol/electrolyte components on gas, liquid, and hydrate phases by using the advantages of the e-CPA EoS to characterize the hydrogen bond association, solvation, ion electrostatic interaction, and ionic solvation. This work has achieved an accurate and flexible way to compute the hydrate formation conditions with or without acid gases, alcohols, and electrolytes. A total of 281 groups of experimental data at pressures from 0.068 MPa to 186.2 MPa are applied to validate this model. The results show that the average relative deviations (ARDs) of predicted temperatures and pressures are 0.13% and 6.52%, respectively. For nonelectrolyte systems, the ARD between the experimental and calculated hydrate formation temperatures is 0.19%, which is reduced by 0.24% and 0.34% in comparison with traditional Soave–Redlich–Kwong and Peng–Robinson EoSs. For mixtures containing alcohol and/or electrolytes, the ARD of predicted hydrate temperatures is 0.12%. Particularly, for harsh systems with ultrahigh pressure (186.2 MPa), the sour gas content of 24.52 mol%, MeOH concentration of 50% by mass, and salinity of 31% by mass, the deviations are less than 2.2 K. More cases demonstrate the performance and synergistic effect of alcohol and electrolytes in inhibiting hydrate formation.