Carbonic Anhydrase‐Mimetic Bolaamphiphile Self‐Assembly for CO2 Hydration and Sequestration

A biomimetic catalyst was prepared through the self‐assembly of a bolaamphiphilic molecule with histidine moieties for the sequestration of carbon dioxide. The histidyl bolaamphiphilic molecule bis(N‐α‐amidohistidine)‐1,7‐heptane dicarboxylate has been synthesized and self‐assembled to produce analogues of the active sites of carbonic anhydrase (CA) after association with Zn²⁺ ions. Spectroscopic analysis demonstrated the coordination of the Zn²⁺ ions with histidine imidazole moieties, which is the core conformation of CA active sites. The Zn‐associated self‐assembly worked as a CA‐mimetic catalyst that shows catalytic activity for CO₂ hydration. Evaluation of the kinetics of using para‐nitrophenylacetate revealed that the kinetic parameters of the CA‐mimetic catalyst were maximized at the optimal Zn concentration and that excess Zn ions resulted in deteriorated catalytic activity. The performance of the CA‐mimetic catalyst was enhanced by changing the pH value and temperature of the reaction, which implies that the hydrolysis of the substrate is the rate‐determining step. The catalyst‐assisted sequestration of CO₂ was demonstrated by CaCO₃ precipitation upon the addition of Ca²⁺ ions. This study offers an easy way to prepare enzyme analogues for CO₂ sequestration through the self‐assembly of bolaamphiphile molecules with designer biochemical moieties.     

A Highly Compatible Phototrophic Community for Carbon-Negative Biosynthesis

CO₂ sequestration engineering is promising for carbon-negative biosynthesis, and artificial communities can solve more complex problems than monocultures. However, obtaining an ideal photosynthetic community is still a great challenge. Herein, we describe the development of a highly compatible photosynthetic community (HCPC) by integrating a sucrose-producing CO₂ sequestration module and a super-coupled module. The cyanobacteria CO₂ sequestration module was obtained using stepwise metabolic engineering and then coupled with the efficient sucrose utilization module Vibrio natriegens. Integrated omics analysis indicated that enhanced photosynthetic electron transport and extracellular vesicles promote intercellular communication. Additionally, the HCPC was used to channel CO₂ into valuable chemicals, enabling the overall release of −22.27 to −606.59 kgCO₂e kg⁻¹ in the end products. This novel light-driven community could facilitate circular economic implementation in the future.     

Carbonic Anhydrase Immobilized on Encapsulated Magnetic Nanoparticles for CO2 Sequestration

Bovine carbonic anhydrase (BCA) was covalently immobilized onto OAPS (octa(aminophenyl)silsesquioxane)‐functionalized Fe₃O₄/SiO₂ nanoparticles by using glutaraldehyde as a spacer. The Fe₃O₄ nanoparticles were coated with SiO₂, onto which was grafted OAPS, and the product was characterized using SEM, TEM, XRD, IR, X‐ray photoelectron spectroscopy (XPS), and magnetometer analysis. The enzymatic activities of the free and Fe₃O₄/SiO₂/OAPS‐conjugated BCA (Fe? CA) were investigated by hydrolyzing p‐nitrophenylacetate (p‐NPA), and hydration and sequestration of CO₂ to CaCO₃. The CO₂ conversion efficiency and reusability of the Fe? CA were studied before and after washing the recovered Fe? CA by applying a magnetic field and quantifying the unreacted Ca²⁺ ions by using ion chromatography. After 30 cycles, the Fe? CA displayed strong activity, and the CO₂ capture efficiency was 26‐fold higher than that of the free enzyme. Storage stability studies suggested that Fe? CA retained nearly 82 % of its activity after 30 days. Nucleation of the precipitated CaCO₃ was monitored by using polarized light microscopy, which revealed the formation of two phases, calcite and valerite, at pH 10 upon addition of serine. The magnetic nanobiocatalyst was shown to be an excellent reusable catalyst for the sequestration of CO_2.     

Effect of polyethyleneglycol (PEG) on gas permeabilities and permselectivities in its cellulose acetate (CA) blend membranes

The effect of polyethyleneglycol (PEG) on gas permeabilities and selectivities was investigated in a series of miscible cellulose acetate (CA) blend membranes. The permeabilities of CO₂, H₂, O₂, CH₄, N₂ were measured at temperatures from 30 to 80°C and pressures from 20 to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane having 10 wt% PEG20000 exhibited higher permeability for CO₂ and higher permselectivity for CO₂ over N₂ and CH₄ than those of the membranes which contained 10% PEG of the molecular weight in the range 200–6000. The CA blend containing 60 wt% PEG20000 showed that its permeability coefficients of CO₂ and ideal separation factors for CO₂ over N₂ reached above 2 × 10⁻⁸ [cm³ (STP) cm/cm² s cmHg] and 22, respectively, at 70°C and 20 cmHg. Based on the data of gas permeability coefficients, time lags and characterization of the membranes, it is proposed that the apparent solubility coefficients of all CA and PEG blend membranes for CO₂ were lower than those of the CA membrane. However, almost all the blend membranes containing PEG20000 showed higher apparent diffusivity coefficients for CO₂, resulting in higher permeability coefficients of CO₂ with relation to those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG20000 blend membranes that their ideal separation factors for CO₂ over N₂ were higher than those of the CA membrane in the range 50–80°C, even though the ideal separation factors of almost all PEG blend membranes for CO₂ over CH₄ became lower than those of the CA membrane over nearly the full range from 30° to 80°C.     

Solvent extraction and radiometric determination of3H-stobadine in biological material

A simple and rapid radiochemical method for the efficient and selective isolation of³H-stobadine from plasma, urine and organ homogenates has been developed. The method comprises the extraction of³H-stobadine from the biological matrix containing 2M Na₂CO₃ into n-hexane followed by scrubbing of partly coextracted metabolites into an equal volume of 2M Na₂CO₃. The specificity of the procedure presented is demonstrated by TLC and the comparison of distribution coefficients of authentic and apparent (isolated) substances.     

Enhanced‐fluidity liquid chromatography using mixed‐mode hydrophilic interaction liquid chromatography/strong cation‐exchange retention mechanisms

The potential of enhanced‐fluidity liquid chromatography, a subcritical chromatography technique, in mixed‐mode hydrophilic interaction/strong cation‐exchange separations is explored, using amino acids as analytes. The enhanced‐fluidity liquid mobile phases were prepared by adding liquefied CO₂ to methanol/water mixtures, which increases the diffusivity and decreases the viscosity of the mixture. The addition of CO₂ to methanol/water mixtures resulted in increased retention of the more polar amino acids. The “optimized” chromatographic performance (achieving baseline resolution of all amino acids in the shortest amount of time) of these methanol/water/CO₂ mixtures was compared to traditional acetonitrile/water and methanol/water liquid chromatography mobile phases. Methanol/water/CO₂ mixtures offered higher efficiencies and resolution of the ten amino acids relative to the methanol/water mobile phase, and decreased the required isocratic separation time by a factor of two relative to the acetonitrile/water mobile phase. Large differences in selectivity were also observed between the enhanced‐fluidity and traditional liquid mobile phases. A retention mechanism study was completed, that revealed the enhanced‐fluidity mobile phase separation was governed by a mixed‐mode retention mechanism of hydrophilic interaction/strong cation‐exchange. On the other hand, separations with acetonitrile/water and methanol/water mobile phases were strongly governed by only one retention mechanism, either hydrophilic interaction or strong cation exchange, respectively.     

Carbon Dioxide‐Controlled Assembly of Water‐Soluble Conjugated Polymers Catalyzed by Carbonic Anhydrase

The CO₂‐responsive and biocatalytic assembly based on conjugated polymers has been demonstrated by combining the signal amplification property of the polythiophene derivative (PTP) and the catalytic actions of carbonic anhydrase (CA). CO₂ is applied as a new trigger mode to construct the smart assembly by controlling the electrostatic and hydrophobic interactions between the PTP molecules in aqueous solution, leading to the visible fluorescence changes. Importantly, the assembly transformation of PTP can be specifically and highly accelerated by CA based on the efficient catalytic activity of CA for the inter‐conversion between CO₂ and HCO₃⁻, mimicking the CO₂‐associated biological processes that occurred naturally in living organisms. Moreover, the PTP‐based assembly can be applied for biomimetic CO₂ sequestration with fluorescence monitoring in the presence of CA and calcium.

     

Enhanced fluidity liquid chromatography for hydrophilic interaction separation of nucleosides

The application of enhanced fluidity liquid (EFL) mobile phases to improving isocratic chromatographic separation of nucleosides in hydrophilic interaction liquid chromatography (HILIC) mode is described. The EFL mobile phase was created by adding carbon dioxide to a methanol/buffer solution. Previous work has shown that EFL mobile phases typically increase the efficiency and the speed of the separation. Herein, an increase in resolution with the addition of carbon dioxide is also observed. This increase in resolution was achieved through increased selectivity and retention with minimal change in separation efficiency. The addition of CO₂ to the mobile phase effectively decreases its polarity, thereby promoting retention in HILIC. Conventional organic solvents of similar nonpolar nature cannot be used to achieve similar results because they are not miscible with methanol and water. The separation of nucleosides with methanol/aqueous buffer/CO₂ mobile phases was also compared to that using acetonitrile/buffer mobile phases. A marked decrease in the necessary separation time was noted for methanol/aqueous buffer/CO₂ mobile phases compared to acetonitrile/buffer mobile phases. There was also an unusual reversal in the elution order of uridine and adenosine when CO₂ was included in the mobile phase.     

Carbonic Anhydrase Facilitated CO2 Diffusion Studied by Means of an Ammonia Sensing Urease Electrode

Abstract

In the present work the influence of carbonic anhydrase (CA) on the gaseous exchanges of CO₂ and NH₃ in a buffered solution has been studied by means of a potentiometric technique involving the use of an urease sensor, whose sensing element was a commercial pNH₃ gas sensing electrode. As pointed out in previous works, suitable experimental conditions were chosen in order to have a speed of CO₂ diffusion sharply enhanced by CA. In particular the analytical aspect of NH₃ production from a buffered urea solution, in the presence and in the absence of CA, is considered.

The results obtained in the present work indicate a further possible application of this system to the study of living organism and tangibly support all the previous studies presented on this topic.     

Highly Efficient CO2 Utilization via Aqueous Zinc– or Aluminum–CO2 Systems for Hydrogen Gas Evolution and Electricity Production

Atmospheric carbon dioxide (CO₂) has increased from 278 to 408 parts per million (ppm) over the industrial period and has critically impacted climate change. In response to this crisis, carbon capture, utilization, and storage/sequestration technologies have been studied. So far, however, the economic feasibility of the existing conversion technologies is still inadequate owing to sluggish CO₂ conversion. Herein, we report an aqueous zinc– and aluminum–CO₂ system that utilizes acidity from spontaneous dissolution of CO₂ in aqueous solution to generate electrical energy and hydrogen (H₂). The system has a positively shifted onset potential of hydrogen evolution reaction (HER) by 0.4 V compared to a typical HER under alkaline conditions and facile HER kinetics with low Tafel slope of 34 mV dec^?1. The Al–CO₂ system has a maximum power density of 125 mW cm^?2 which is the highest value among CO₂ utilization electrochemical system.     

Recent advances in chemical fixation of CO2 based on flow chemistry

Carbon dioxide (CO₂) is an attractive C1 building block in chemical synthesis due to its abundance, availability and sustainability. However, the low reactivity and high stability generally limits its transformations under mild conditions to value added chemicals. Recent advances in flow chemistry provide effective means for the chemical transformation of CO₂, and many new methods and techniques that fully utilized the advantages of continuous flow platforms for the chemical fixation of CO₂ have been realized. In view of the rapid development and the urgent need for continuous transformation of CO₂, herein we wish to present an update of the recent advances in this research area.     

Preliminary studies of supercritical-fluid chromatography on porous graphitic carbon with methylated cyclodextrin as chiral selector

Summary Dimethylated-β-cyclodextrins dynamically adsorbed on porous graphitic carbon have been used as chiral selectors in chiral supercritical-(or subcritical-) fluid chromatography. The kinetics of adsorption and desorption were studied with CO₂-methanol+dimethylated-β-cyclodextrins and CO₂-methanol as mobile phases. The system was proved to be stable and reproducible and to afford rapid enantiomer separations especially when performed with 95:5 CO₂-methanol+dimethylated-β-cyclodextrin as mobile phase. The versatility of the chiral system enabled the use of a variety of chiral selectors. It was found that enantiomer separation can vary largely as a function of the composition of commercial dimethylated-β-cyclodextrin mixture.     

Dissolution and dispersion of CO2 from a liquid CO2 pool in the deep ocean

Liquid CO₂ sequestration in a bathymetric depression at depths greater than 3700 m in the ocean has been proposed as a mitigation strategy for the reduction of atmospheric CO₂ emissions. Kinetic studies on the dissolution of CO₂ from the liquid CO₂ pool, the diffusion in the ocean, and advection of CO₂ by the bottom ocean current are carried out. A thin membrane of CO₂ hydrate on the liquid CO₂ pool controls the CO₂ dissolution into the overlaying seawater, the thickness of a static layer between the surface of liquid CO₂ and the upper bottom ocean current reduces the CO₂ diffusion, and the bottom ocean current dilutes the CO₂ concentration. These effects are explicity formulated in an equation, and it is predicted that ocean CO₂ sequestration at a depth larger than 3700 m will greatly reduce the pH change caused by CO₂ dispersion in the ocean. © 1995 John Wiley & Sons, Inc.     

Adsorption technology for CO2 separation and capture: a perspective

The capture of CO₂ from process and flue gas streams and subsequent sequestration was first proposed as a greenhouse gas mitigation option in the 1990s. This proposal spawned a series of laboratory and field tests in CO₂ capture which has now grown into a major world-wide research effort encompassing a myriad of capture technologies and ingenious flow sheets integrating power production and carbon capture. Simultaneously, the explosive growth in materials science in the last two decades has produced a wealth of new materials and knowledge providing us with new avenues to explore to fine tune CO₂ adsorption and selectivity. Laboratory and field studies over the last decade have explored the synergy of process and materials to produce numerous CO₂ capture technologies and materials based on cyclic adsorption processes. In this brief perspective, we look at some of these developments and comment on the application and limitations of adsorption process to CO₂ capture. We identify major engineering obstacles to overcome as well as potential breakthroughs necessary to achieve commercialization of adsorption processes for CO₂ capture. Our perspective is primarily restricted to post-combustion flue gas capture and CO₂ capture from natural gas.     

Adsorption technology for direct recovery of compressed,pure CO<Subscript>2</Subscript> from a flue gas without pre-compression or pre-drying

The effects of the sorption and the regeneration temperatures on the performance of a novel rapid thermal swing chemisorption (RTSC) process (Lee and Sircar in AIChE J. 54:2293–2302, 2008) for removal and recovery of CO₂ from an industrial flue gas without pre-compression, pre-drying, or pre-cooling of the gas were mathematically simulated. The process directly produced a nearly pure, compressed CO₂ by-product stream which will facilitate its subsequent sequestration. Na₂O promoted alumina was used as the CO₂ selective chemisorbent, and the preferred temperatures were found to be, respectively, 150 and 450 °C for the sorption and regeneration steps of the process. The specific cyclic CO₂ production capacity of the process and the pressure of the by-product CO₂ gas were substantially increased over those previously achieved by using the sorption and regeneration temperature of, respectively, 200 and 500 °C (Lee and Sircar in AIChE J. 54:2293–2302, 2008). The net compressed CO₂ recovery from the flue gas (∼92%) did not change. However, substantially different amounts of high and low pressure steam purges were necessary for comparable degree of desorption of CO₂. A first pass estimation of the capital and the operating costs of the RTSC process was carried out for a relatively moderate size application (flue gas clean up and CO₂ recovery from a ∼80 MW coal fired power plant). Both costs were substantially lower than those for a conventional absorption process using MEA as the CO₂ solvent (Desideri and Paolucci in Energy Convers. Manag. 40:1899–1915, 1999).     

Quantitative High Performance Liquid Chromatography Determination of Alkanolamines in Ionic Liquid Absorbents

The development of modern absorption media suitable for CO₂ scrubbing, such as ionic liquids and their mixtures, requires appropriate analytical protocols. In this paper, the application of high-performance liquid chromatography to the determination of alkanolamine at various concentrations in ionic liquid solutions was investigated. Both hydrophilic and hydrophobic commercial ionic liquids, such as 1-butyl-3-methylimidazolium acetate [bmim][OAc], 1-ethyl-3-methylimidazolium octylsulfate [emim][OcSO₄], and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [bmim][NTf₂], were studied in this paper and different sample preparation procedures were used for each class of solvent. A simple extraction step was necessary prior to HPLC analysis for hydrophobic ionic liquids. This step was performed using five times more 0.05 M KH₂PO₄ than needed for the ionic liquid sample. Hydrophilic ionic liquid solutions could be analyzed after diluting the sample with water. The general procedure involved separation at room temperature using a cation-exchange HPLC with 0.05 M KH₂PO₄ as the mobile phase and refractometric detection without derivatizing the amines. The influence of the temperature and mobile phase composition on alkanolamine retention was investigated. The relationship between the peak area and alkanolamine concentration was linear over 3 orders of magnitude (2–200 nmol). The detection limit (LOD) for monoethanolamine (MEA) and diethanolamine (DEA) was 1.5 and 2 nmol, respectively. For hydrophobic ionic liquids, which require extraction, it was possible to analyze a 0.004% MEA solution. The quantity of the sample required for analysis was 0.1 g, and the analysis time did not exceed 20 minutes.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO₂-H₂O system. Experiments run in the solutions equilibrated with various CO₂ partial pressures (P_{CO 2} ) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO₂ conversion. However, great differences occur among various CO₂ partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various P_{CO 2} with satisfactory precision at least far from equilibrium.     

Kinetics and rate-limiting mechanisms of dolomite dissolution at various CO2 partial pressures

Techniques of rotating-disk and catalyst were used in investigating the kinetics of dolomite dissolution in flowing CO₂-H₂O system. Experiments run in the solutions equilibrated with various CO₂ partial pressures (P_{CO 2} ) from 30 to 100000 Pa. It shows that dissolution rates of dolomite are related with rotating speeds at conditions far from equilibrium. This was explained by modified diffusion boundary layer (DBL) model. In addition, the dissolution rates increase after addition of carbonic anhydrase (CA) to solutions, where the CA catalyzes CO₂ conversion. However, great differences occur among various CO₂ partial pressures. The experimental observations give a conclusion that the modified DBL model enables one to predict dissolution rates and their behaviour at various P_{CO 2} with satisfactory precision at least far from equilibrium.     

Sequestration of CO2 using Cu nanoparticles supported on spherical and rod-shape mesoporous silica

The CO₂ sequestration is one of the most promising solutions to tackle global warming. In this study, spherical mesoporous silica particles (MPS-S) and rod-shaped mesoporous silica particles (MPS-R) loaded with Cu nanoparticles were selectively prepared and employed for CO₂ adsorption. For the first time uniform Cu nanoparticles were incorporated into the rod-shaped mesoporous silica particles by post-synthesis modification using both N-[3-(trimethoxysilyl)propyl]ethylenediamine (PEDA) and ethylenediamine (EDA) as coupling agents. The physiochemical properties of the mesoporous and copper grifted silica composites were investigated by CHN elemental analysis, FTIR spectroscopy, thermogravimetric analysis, X-ray diffraction, energy dispersive X-ray spectroscopy (EDX), surface area analysis, scanning, transmission electron microscopy and gas analysis system (GSD 320, TERMO). The mesoporous silica shows highly ordered mesoporous structures, with the rod-shaped particles having a higher surface area than the spherical ones. Copper nanoparticles with an average diameter of 6.0 nm were uniformly incorporated into the MPS-S and MPS-R. Moreover, Cu-loaded mesoporous silica exhibits up to 40% higher CO₂ adsorption capacity than the bare MPS. The MPS-R modified with Cu nanoparticles showed a maximum CO₂ adsorption capacity of 0.62 mmol/g and the humidity showed a slight negative effect on CO₂ uptake process. The enhancement of CO₂ adsorption onto transition metal/mesoporous substrates provides basis for imminent CO₂ sequestration.     

Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO2 to CO

Rising atmospheric CO₂ is expected to have negative effects on the global environment from its role in climate change and ocean acidification. Utilizing CO₂ as a feedstock to make valuable chemicals is potentially more desirable than sequestration. A substantial reduction of CO₂ levels requires a large‐scale CO₂ catalytic conversion process, which in turn requires the discovery of low‐cost catalysts. Results from the current study demonstrate the feasibility of using the non‐precious metal material molybdenum carbide (Mo₂C) as an active and selective catalyst for CO₂ conversion by H₂.