Facile Fabrication of Monodispersed Carbon Sphere: A Pathway Toward Energy-Efficient Direct Air Capture (DAC) Using Amino Acids.

Direct removal of carbon dioxide (CO2 ) from the atmosphere, known as direct air capture (DAC) is attracting worldwide attention as a negative emission technology to control atmospheric CO2 concentrations. However, the energy-intensive nature of CO2 absorption-desorption processes has restricted deployment of DAC operations. Catalytic solvent regeneration is an effective solution to tackle this issue by accelerating CO2 desorption at lower regeneration temperatures. This work reports a one-step synthesis methodology to prepare monodispersed carbon nanospheres (MCSs) using trisodium citrate as a structure-directing agent with acidic sites. The assembly of citrate groups on the surface of MCSs enables consistent spherical growth morphology, reduces agglomeration and enhances water dispersibility. The functionalization-assisted synthesis produces uniform, hydrophilic nanospheres of 100-600 nm range. This work also demonstrates that the prepared MCSs can be further functionalized with strong Brønsted acid sites, providing high proton donation ability. Furthermore, the materials can be effectively used in a wide range of amino acid solutions to substantially accelerate CO2 desorption (25.6% for potassium glycinate and 41.1% for potassium lysinate) in the DAC process. Considering the facile synthesis of acidic MCSs and their superior catalytic efficiency, these findings are expected to pave a new path for energy-efficient DAC.

Cytochrome P450-mediated N-demethylation of noscapine by whole-cell biotransformation: process limitations and strategies for optimisation.

Cytochrome P450 enzymes catalyse reactions of significant industrial interest but are underutilised in large-scale bioprocesses due to enzyme stability, cofactor requirements and the poor aqueous solubility and microbial toxicity of typical substrates and products. In this work, we investigate the potential for preparative-scale N-demethylation of the opium poppy alkaloid noscapine by a P450BM3 (CYP102A1) mutant enzyme in a whole-cell biotransformation system. We identify and address several common limitations of whole-cell P450 biotransformations using this model N-demethylation process. Mass transfer into Escherichia coli cells was found to be a major limitation of biotransformation rate and an alternative Gram-positive expression host Bacillus megaterium provided a 25-fold improvement in specific initial rate. Two methods were investigated to address poor substrate solubility. First, a biphasic biotransformation system was developed by systematic selection of potentially biocompatible solvents and in silico solubility modelling using Hansen solubility parameters. The best-performing biphasic system gave a 2.3-fold improvement in final product titre compared to a single-phase system but had slower initial rates of biotransformation due to low substrate concentration in the aqueous phase. The second strategy aimed to improve aqueous substrate solubility using cyclodextrin and hydrophilic polymers. This approach provided a fivefold improvement in initial biotransformation rate and allowed a sixfold increase in final product concentration. Enzyme stability and cell viability were identified as the next parameters requiring optimisation to improve productivity. The approaches used are also applicable to the development of other pharmaceutical P450-mediated biotransformations.

Dynamic interactions between microbubbles in water.

The interaction between moving bubbles, vapor voids in liquid, can arguably represent the simplest dynamical system in continuum mechanics as only a liquid and its vapor phase are involved. Surprisingly, and perhaps because of the ephemeral nature of bubbles, there has been no direct measurement of the time-dependent force between colliding bubbles which probes the effects of surface deformations and hydrodynamic flow on length scales down to nanometers. Using ultrasonically generated microbubbles (approximately 100 microm size) that have been accurately positioned in an atomic force microscope, we have made direct measurements of the force between two bubbles in water under controlled collision conditions that are similar to Brownian particles in solution. The experimental results together with detailed modeling reveal the nature of hydrodynamic boundary conditions at the air/water interface, the importance of the coupling of hydrodynamic flow, attractive van der Waals-Lifshitz forces, and bubble deformation in determining the conditions and mechanisms that lead to bubble coalescence. The observed behavior differs from intuitions gained from previous studies conducted using rigid particles. These direct force measurements reveal no specific ion effects at high ionic strengths or any special role of thermal fluctuations in film thickness in triggering the onset of bubble coalescence.

Anomalous pull-off forces between surfactant-free emulsion drops in different aqueous electrolytes.

A systematic study of collisions between surfactant-free organic drops in aqueous electrolyte solutions reveals the threshold at which continuum models provide a complete description of thin-film interactions. For collision velocities above ~1 µm/s, continuum models of hydrodynamics and surface forces provide a complete description of the interaction, despite the absence of surfactant. This includes accurate prediction of coalescence at high salt concentration (500 mM). In electrolyte solutions at intermediate salt concentration (50 mM), drop-drop collisions at lower velocity (<1 µm) or extended time of forced drop-drop interaction exhibit a strong pull-off force of systematically varying magnitude. The observations have implications on the effects of ion-specificity and time-dependence in drop-drop interactions where kinetic stability is marginal.

Modification of naturally abundant resources for remediation of potentially toxic elements: A review.

Water and soil contamination due to potentially toxic elements (PTEs) represents a critical threat to the global ecosystem and human health. Naturally abundant resources have significant advantages as adsorbent materials for environmental remediation over manufactured materials such as nanostructured materials and activated carbons. These advantages include cost-effectiveness, eco-friendliness, sustainability, and nontoxicity. In this review, we firstly compare the characteristics of representative adsorbent materials including bentonite, zeolite, biochar, biomass, and effective modification methods that are frequently used to enhance their adsorption capacity and kinetics. Following this, the adsorption pathways and sites are outlined at an atomic level, and an in-depth understanding of the structure-property relationships are provided based on surface functional groups. Finally, the challenges and perspectives of some emerging naturally abundant resources such as lignite are examined. Although both unamended and modified naturally abundant resources face challenges associated with their adsorption performance, cost performance, energy consumption, and secondary pollution, these can be tackled by using advanced techniques such as tailored modification, formulated mixing and reorganization of these materials. Recent studies on adsorbent materials provide a strong foundation for the remediation of PTEs in soil and water. We speculate that the pursuit of effective modification strategies will generate remediation processes of PTEs better suited to a wider variety of practical application conditions.

Engineered assembly of water-dispersible nanocatalysts enables low-cost and green CO2 capture.

Catalytic solvent regeneration has attracted broad interest owing to its potential to reduce energy consumption in CO2 separation, enabling industry to achieve emission reduction targets of the Paris Climate Accord. Despite recent advances, the development of engineered acidic nanocatalysts with unique characteristics remains a challenge. Herein, we establish a strategy to tailor the physicochemical properties of metal-organic frameworks (MOFs) for the synthesis of water-dispersible core-shell nanocatalysts with ease of use. We demonstrate that functionalized nanoclusters (Fe3O4-COOH) effectively induce missing-linker deficiencies and fabricate mesoporosity during the self-assembly of MOFs. Superacid sites are created by introducing chelating sulfates on the uncoordinated metal clusters, providing high proton donation capability. The obtained nanomaterials drastically reduce the energy consumption of CO2 capture by 44.7% using only 0.1 wt.% nanocatalyst, which is a ∽10-fold improvement in efficiency compared to heterogeneous catalysts. This research represents a new avenue for the next generation of advanced nanomaterials in catalytic solvent regeneration.

Precision AFM measurements of dynamic interactions between deformable drops in aqueous surfactant and surfactant-free solutions.

The atomic force microscope (AFM) has provided unprecedented opportunities to study velocity-dependent interactions between deformable drops and bubbles under a range of solution conditions. The challenge is to design an experimental system that enables accurate force spectroscopy of the interaction between deformable drops and thus the extraction of accurate quantitative information about the physically important force-separation relation. This step requires very precise control and knowledge of the interfacial properties of the interacting drops, the drive conditions of the force-sensing cantilever, the disposition of the interacting drops on the substrate and on the cantilever, and transducer calibrations of the instrument in order to quantify the effects of approach velocities and interfacial deformation. This article examines and quantifies in detail all experimental conditions that are necessary to facilitate accurate processing of dynamic force spectroscopy data from the AFM using the well-defined system of tetradecane drops in aqueous solutions under surfactant and surfactant-free conditions over a range of force magnitudes that has not been attained before. The ability of drops to deform and increase the effective area of interaction instead of decreasing the distance of closest approach when disjoining pressure exceeds the Laplace pressure means that the DLVO paradigm of colloidal stability as being determined by a balance of kinetic energy against the height of the primary maximum is no longer valid. The range of interfacially active species present in alkane-aqueous systems investigated provides insight into the applicability of the tangentially immobile boundary condition in colloidal interactions.

Multilayered microspheres for the controlled release of growth factors in tissue engineering.

Tissue regeneration may be stimulated by growth factors but to be effective, this delivery must be sustained and requires delivery vehicles that overcome the short half-life of these molecules in vivo. One promising approach is to couple growth factors to the biomaterial surface so that they are readily bioavailable. Here the layer-by-layer process was used to construct a multilayered polyelectrolyte delivery system on the surface of poly(lactic-co-glycolic) acid constructs. The system was first optimized on a planar surface before translation to a 3D microsphere system. The layers incorporated heparin to facilitate the loading of basic fibroblast growth factor and increase growth factor stability. Cross-linked capping layers also reduced any burst release. The model growth factor was released in a sustained manner and stimulated significantly higher cell proliferation in vitro on release compared with the addition of the growth factor heparin complex free in solution, demonstrating the promise of this approach.

Borate-catalyzed carbon dioxide hydration via the carbonic anhydrase mechanism.

The hydration of CO(2) plays a critical role in carbon capture and geoengineering technologies currently under development to mitigate anthropogenic global warming and in environmental processes such as ocean acidification. Here we reveal that borate catalyzes the conversion of CO(2) to HCO(3)(-) via the same fundamental mechanism as the enzyme carbonic anhydrase, which is responsible for CO(2) hydration in the human body. In this mechanism the tetrahydroxyborate ion, B(OH)(4)(-), is the active form of boron that undergoes direct reaction with CO(2). In addition to being able to accelerate CO(2) hydration in alkaline solvents used for carbon capture, we hypothesize that this mechanism controls CO(2) uptake by certain saline bodies of water, such as Mono Lake (California), where previously inexplicable influx rates of inorganic carbon have created unique chemistry. The new understanding of CO(2) hydration provided here should lead to improved models for the carbon cycle in highly saline bodies of water and to advances in carbon capture and geoengineering technology.

The electro-Fenton regeneration of Granular Activated Carbons: Degradation of organic contaminants and the relationship to the carbon surface.

Electrochemical regeneration of Granular Activated Carbon is an emerging treatment option to restore adsorption capacity in systems designed to remove organic contaminants from aqueous solutions. The electro-Fenton process is one such electrochemical process and it is reviewed along with other members of its family including Photoelectro-Fenton and Heterogeneous electro-Fenton and electro-Fenton like reactions, for its ability to regenerate Granular Activated Carbons contaminated with organics. The behaviour of critical operating parameter such as pH, current, catalyst concentration and initial contaminant concentration are reviewed to find optimal operating conditions. The relationship between electro-Fenton regeneration and the chemical and physical surface of the carbon is also explored. Understanding regeneration mechanisms and the optimal operating conditions enables these technologies to be used commercially and to be scaled-up and treat contaminated waters more efficiently.

Assessment of the electro-Fenton pathway for the removal of naphthalene from contaminated waters in remote regions.

This work investigates the effectiveness of the electro-Fenton reaction for the treatment of wastewaters contaminated with petroleum hydrocarbons. More specific attention was given to field deployment applications in remote regions, such as the sub-Antarctic, where there is a need for low-cost technologies that can aid in remediation efforts. Naphthalene, a high priority pollutant for removal within these regions, was chosen as a model contaminant and treated with inexpensive graphite electrodes to promote the electro-Fenton pathway. Results show that naphthalene can be fully removed from a near-saturated solution, 20 mg/L, in less than 3 h of treatment. The underlying removal mechanisms were identified, and a kinetic model is presented that can accurately predict treatment outcomes at varying operating conditions of applied electric currents, 0-5 mA, and iron(II) concentrations, 0-2.0 mM. Optimal operating conditions for the electro-Fenton pathway were found to be at an applied current of 5 mA and an iron(II) concentration of 0.06 mM; this resulted in a specific energy consumption of 5.6 kWhr/kg of naphthalene removed, low enough to be operated in remote regions via sustainable energy sources.

Adsorption Behavior of Divalent Metal Ions onto Surface-functionalized Mesoporous Silicate MCM-41 Having Schiff Base Structure.

Surface functionalized mesoporous silicates, MCM-41s, having 3-(2-pyridylmethylideneimino)propyl group (PI-MCM-41) or 3-(2-quinolylmethylideneimino)propyl group (QI-MCM-41) were prepared via Schiff base reaction, and the adsorption behavior of metal ions onto the modified MCM-41s was investigated. The function groups on the modified MCM-41 surface were confirmed by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis. The metal ions examined, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+, were quantitatively adsorbed on the PI-MCM-41 and QI-MCM-41, except for Mn2+. In the complexation with these metal ions, it was suggested that imine-N and heterocyclic-N atoms act as donor atoms. In addition, it was considered that the hydrophobicity derived from the organo-functional groups modified on MCM-41 contributed to improving the adsorption ability.

Water-Dispersible Nanocatalysts with Engineered Structures: The New Generation of Nanomaterials for Energy-Efficient CO2 Capture.

The high energy demand of CO2 absorption-desorption technologies has significantly inhibited their industrial utilization and implementation of the Paris Climate Accord. Catalytic solvent regeneration is of considerable interest due to its low operating temperature and high energy efficiency. Of the catalysts available, heterogeneous catalysts have exhibited relatively poor performances and are hindered by other challenges, which have slowed their large-scale deployment. Herein, we report a facile and eco-friendly approach for synthesizing water-dispersible Fe3O4 nanocatalysts coated with a wide range of amino acids (12 representative molecules) in aqueous media. The acidic properties of water-dispersible nanocatalysts can be easily tuned by introducing different functional groups during the hydrothermal synthesis procedure. We demonstrate that the prepared nanocatalysts can be used in energy-efficient CO2 capture plants with ease-of-use, at very low concentrations (0.1 wt %) and with extra-high efficiencies (up to ∼75% energy reductions). They can be applied in a range of solutions, including amino acids (i.e., short-chain, long-chain, and cyclic) and amines (i.e., primary, tertiary, and primary-tertiary mixture). Considering the superiority of the presented water-dispersible nanocatalysts, this technology is expected to provide a new pathway for the development of energy-efficient CO2 capture technologies.

Viscosity effects on hydrodynamic drainage force measurements involving deformable bodies.

Dynamic force measurements have been made between an oil drop and a silica particle in surfactant and sucrose solutions with viscosities that range up to 50 times that of water. These conditions provide variations in the shear rate and the relative time scales of droplet deformation and hydrodynamic drainage in a soft matter system. The results obtained indicate that soft deformable boundaries have a natural response that limits the maximum shear rate that can be sustained in thin films compared to shear rates that can be attained in films bounded by rigid boundaries. In addition, to extend boundary slip studies on rigid surfaces, we use a smooth deformable droplet surface to probe the dependence of the boundary slip on fluid viscosity without the added complications of surface roughness or heterogeneity. Imposing a Navier slip model to characterize possible slip at the deformable oil-sucrose solution interface gives results that are consistent with a slip length of no larger than 10 nm over the range of solution viscosity studied, although an immobile (zero slip length) condition at the oil-sucrose solution interface is perfectly adequate. In high viscosity solutions, cantilever motion at high scan rates induces a significant cantilever deflection. A method has been developed to account for this effect in order to extract the correct dynamic force between the deformable drop and the particle.

Lateral hydrodynamic interactions between an emulsion droplet and a flat surface evaluated by frictional force microscopy.

We introduce a lateral atomic force microscopy (AFM) method to measure the hydrodynamic drag force acting on a microscopic emulsion droplet moving parallel to a flat surface. A tetradecane oil droplet formed in an aqueous solution of sodium dodecylsulfate was attached to a V-shaped atomic force microscopy cantilever, and lateral hydrodynamic interactions between the droplet and a flat glass surface were measured using a range of scanning velocities. The droplet was positioned either far from the oscillating surface or was pressed to the surface under a constant applied load. These measurements demonstrate the feasibility of using AFM to study lateral hydrodynamic interactions and lubricity between soft matter materials relevant to a large number of applications in areas as diverse as flavor delivery in foods to the applications of emulsions or emollients in personal care products.

Electrochemical removal of naphthalene from contaminated waters using carbon electrodes, and viability for environmental deployment.

This work assesses the potential of electrochemical technologies for the treatment of groundwaters contaminated with petroleum hydrocarbons. Specific consideration was given to deployment in Antarctic regions where numerous fuel spills have occurred over the last two centuries, and resources and manual labour for remediation efforts are limited. The polycyclic aromatic hydrocarbon, naphthalene, was a used as a model contaminant and was treated with low-cost, active carbon electrodes to promote the active chlorine degradation pathway. Results showed that 20 mg/L naphthalene solutions could be treated to sufficient standards in less than 3 h of treatment, and that the formation of toxic and chlorinated by-products is not an issue of concern if the appropriate timeframes are used (4 h of treatment). The effects of the applied current (0-160 mA) and electrolyte concentration (0.01-0.1 M NaCl) were evaluated and a dynamic kinetic model proposed and found to be in good agreement with the experimental results. The energy consumption is an important limitation in remote environmental regions where resources are scarce. It was found that an energy usage of 104 kW h/kg of naphthalene removed could be achieved.

High-Efficiency Biocatalytic Conversion of Thebaine to Codeine.

An enzymatic biosynthesis approach is described for codeine, the most widely used medicinal opiate, providing a more environmentally sustainable alternative to current chemical conversion, with yields and productivity compatible with industrial production. Escherichia coli strains were engineered to express key enzymes from poppy, including the recently discovered neopinone isomerase, producing codeine from thebaine. We show that compartmentalization of these enzymes in different cells is an effective strategy that allows active spatial and temporal control of reactions, increasing yield and volumetric productivity and reducing byproduct generation. Codeine is produced at a yield of 64% and a volumetric productivity of 0.19 g/(L·h), providing the basis for an industrially applicable aqueous whole-cell biotransformation process. This approach could be used to redirect thebaine-rich feedstocks arising from the U.S. reduction of opioid manufacturing quotas or applied to enable total biosynthesis and may have broader applicability to other medicinal plant compounds.

Spectroscopic studies of molecular interaction at the liquid-liquid interface.

The development of techniques to study the liquid-liquid interface is a major challenge. Spectroscopy in all its forms provides a powerful method of investigation, especially when combined with other optical techniques. Over the last 30 years, there have been significant developments in the methods for studying heterogeneous interfaces. As technology progresses, the sensitivity of existing techniques has been improved but there are major challenges still to be met, such as the measurement of interfacial dielectric constant and viscosity. This paper aims to summarise the use of spectroscopy to study molecular interactions at the liquid-liquid interface.

Data in brief on CO2 absorption-desorption of aqueous-based amino acid solvents with phase change behaviour.

The data presented in this paper are related to the published research article "Development of aqueous-based phase change amino acid solvents for energy-efficient CO2 capture: The role of antisolvent" [1]. The raw and analyzed data include the equilibrium and kinetics of CO2 absorption, the density and concentration of different CO2-containing species at upper and lower liquid phases, and particle size distribution of solid particles precipitated during CO2 absorption of aqueous and aqueous-based amino acid solvents. In addition, the SEM images of solid precipitates at the end of CO2 absorption are presented. The detailed values of this phase change amino acid solvent are crucial for large-scale implementation of CO2 capture systems with phase change behavior.

Production of metabolites of the anti-cancer drug noscapine using a P450BM3 mutant library.

Cytochrome P450 enzymes are a promising tool for the late-stage diversification of lead drug candidates and can provide an alternative route to structural modifications that are difficult to achieve with synthetic chemistry. In this study, a library of P450BM3 mutants was produced using site-directed mutagenesis and the enzymes screened for metabolism of the opium poppy alkaloid noscapine, a drug with anticancer activity. Of the 18 enzyme mutants screened, 12 showed an ability to metabolise noscapine that was not present in the wild-type enzyme. Five noscapine metabolites were detected by LC-MS/MS, with the major metabolite for all mutants being N-demethylated noscapine. The highest observed regioselectivity for N-demethylation was 88%. Two hydroxylated metabolites, a catechol and two C-C cleavage products were also detected. P450-mediated production of hydroxylated and N-demethylated noscapine structures may be useful for the development of noscapine analogues with improved biological activity. The variation in substrate turnover, coupling efficiency and product distribution between the active mutants was considered alongside in silico docking experiments to gain insight into structural and functional effects of the introduced mutations. Selected mutants were identified as targets for further mutagenesis to improve activity and when coupled with an optimised process may provide a route for the preparative-scale production of noscapine metabolites.