Aqueous Bulk Research Articles

Impact of electrolyte on the structure and orientation of water at air/water-polyethylene glycol polymer interface.

Polyethylene glycol (PEG) is a water soluble, non-ionic polymer with applications in drug delivery, protein precipitation, anti-biofouling, water-splitting, Li-ion batteries, and fuel cells. The interaction of PEG with water and electrolytes plays pivotal roles in such applications. Using interface-selective spectroscopy, heterodyne-detected vibrational sum frequency generation, and Raman difference spectroscopy with simultaneous curve fitting analysis, we show that water adopts different structures and orientations at the air/water-PEG interface, which depends on the molar mass of the PEG. At the air/water-PEG4000 (MW 4000u) interface, water is H-up oriented (i.e., water Hs are pointed away from the aqueous bulk) around 3200cm-1 and H-down oriented (i.e., water Hs are pointed toward the aqueous bulk) around 3470cm-1. Variation of the bulk concentration of PEG4000 does not change the dual orientation of interfacial water. The presence of an electrolyte (1.0M NaCl) selectively reduces the H-up oriented water without affecting the H-down oriented water at the air/water-PEG4000 interface. The selective reorganization of the interfacial water is assigned to the disruption of the asymmetric hydration around ether-oxygen of the surface-adsorbed PEG4000 by the Na+ ion of the electrolyte. Interestingly, in the case of low molar mass PEG (air/water-PEG200), the interfacial water neither shows the dual orientation nor is affected by 1.0M NaCl.

Casein network formation at oil–water interfaces is reduced by [formula omitted]-casein and increased by Ca[formula omitted]

Mixtures of bovine caseins can serve as a benchmark for understanding the functionality of microbial-based recombinant caseins at oil–water interfaces. In this work we show that, in the presence of Ca2+, the individual casein fractions form viscoelastic networks at the oil–water interface with comparable stiffness. In the absence of Ca2+, αs2- and β-casein interfacial network formation was strongly inhibited over the full deformation regime. For αs1-casein, the network stiffness was increased in the absence of Ca2+ at small deformations (<15%), but at large deformations (>50%) it was completely disrupted, to a similar stiffness as αs2- and β-casein. The interfacial structure formed by κ-casein was largely unaffected by Ca2+ due to limited phosphorylation. We hypothesize that the differences between calcium-sensitive caseins lie in the conformation they assume at the interface. Both αs2- and β-casein adsorb in a train-tail conformation with a tail extending into the aqueous bulk phase, whereas αs1-casein adsorbs in a loop-train conformation, with a loop that extends less into the bulk phase. The tail-train configuration is hypothesized to increase the inter-molecular Ca2+ bridging thereby increasing the interfacial stiffness of αs2- and β-casein.Blending the casein fractions revealed a strong negative effect of β-casein on the interfacial modulus, which was more pronounced at a higher concentration. The presence of Ca2+ remained important for interfacial network formation of a casein blend. Without Ca2+, the interfacial network was less stiff, more viscous, and behaved like a 2d polymer solution.With this work we showed that casein interfacial network formation at oil–water interfaces is mediated by Ca2+ bridging. Blending the different casein fractions decreased the interfacial viscoelastic properties through the presence of β-casein. These results indicate that future work on recombinant caseins should focus on single genetic variants, since a blend of variants will likely decrease interfacial functionality.

MgO-loaded tubular ceramic membrane with spatial nanoconfinement for enhanced catalytic ozonation in refractory wastewater treatment

Heterogeneous catalytic ozonation (HCO) enables the destruction of organic pollutants in wastewater via oxidation by powerful hydroxyl radicals (·OH). However, the availability of short‐lived ·OH in aqueous bulk is low in practical treatment scenarios due to mass transfer limitations and quenching of water constituents. Herein, we overcome these challenges by loading MgO catalysts inside the pores of a tubular ceramic membrane (denoted as CCM) to confine ·OH within the nanopores and achieve efficient pollutant removal. When the pore size of the membrane was reduced from 1000 to 50 nm, the removal of ibuprofen (IBU) by CCM was increased from 49.6 % to 90.2 % due to the enhancement of ·OH enrichment in the nanospace. In addition, the CCM exhibited high catalytic activity in the presence of co-existing ions and over a wide pH range, as well as good self-cleaning ability in treating secondary wastewater. The experimental results revealed that ·OH were the dominant reactive oxygen species (ROS) in pollutant degradation, while surface hydroxyl groups were active sites for the generation of ·OH via ozone decomposition. This work provides a promising strategy to enhance the utilization of ·OH in HCO for the efficient degradation of organic pollutants in wastewater under spatial confinement.

Investigating the mechanism of interfacial tension reduction through the combination of low-salinity water and bacteria

In the enhanced oil recovery (EOR) process, interfacial tension (IFT) has become a crucial factor because of its impact on the recovery of residual oil. The use of surfactants and biosurfactants can reduce IFT and enhance oil recovery by decreasing it. Asphaltene in crude oil has the structural ability to act as a surface-active material. In microbial-enhanced oil recovery (MEOR), biosurfactant production, even in small amounts, is a significant mechanism that reduces IFT. This study aimed to investigate fluid/fluid interaction by combining low biosurfactant values and low-salinity water using NaCl, MgCl2, and CaCl2 salts at concentrations of 0, 1000, and 5000 ppm, along with Geobacillus stearothermophilus. By evaluating the IFT, this study investigated different percentages of 0, 1, and 5 wt.% of varying asphaltene with aqueous bulk containing low-salinity water and its combination with bacteria. The results indicated G. Stearothermophilus led to the formation of biosurfactants, resulting in a reduction in IFT for both acidic and basic asphaltene. Moreover, the interaction between asphaltene and G. Stearothermophilus with higher asphaltene percentages showed a decrease in IFT under both acidic and basic conditions. Additionally, the study found that the interaction between acidic asphaltene and G. stearothermophilus, in the presence of CaCl2, NaCl, and MgCl2 salts, resulted in a higher formation of biosurfactants and intrinsic surfactants at the interface of the two phases, in contrast to the interaction involving basic asphaltene. These findings emphasize the dependence of the interactions between asphaltene and G. Stearothermophilus, salt, and bacteria on the specific type and concentration of asphaltene.

Enrichment of different taxa of the enigmatic candidate phyla radiation bacteria using a novel picolitre droplet technique.

The candidate phyla radiation (CPR) represents a distinct monophyletic clade and constitutes a major portion of the tree of life. Extensive efforts have focused on deciphering the functional diversity of its members, primarily using sequencing-based techniques. However, cultivation success remains scarce, presenting a significant challenge, particularly in CPR-dominated groundwater microbiomes characterized by low biomass. Here, we employ an advanced high-throughput droplet microfluidics technique to enrich CPR taxa from groundwater. Utilizing a low-volume filtration approach, we successfully harvested a microbiome resembling the original groundwater microbial community. We assessed CPR enrichment in droplet and aqueous bulk cultivation for 30days using a novel CPR-specific primer to rapidly track the CPR fraction through the cultivation attempts. The combination of soil extract and microbial-derived necromass provided the most supportive conditions for CPR enrichment. Employing these supplemented conditions, droplet cultivation proved superior to bulk cultivation, resulting in up to a 13-fold CPR enrichment compared to a 1- to 2-fold increase in bulk cultivation. Amplicon sequencing revealed 10 significantly enriched CPR orders. The highest enrichment in CPRs was observed for some unknown members of the Parcubacteria order, Cand. Jorgensenbacteria, and unclassified UBA9983. Furthermore, we identified co-enriched putative host taxa, which may guide more targeted CPR isolation approaches in subsequent investigations.

Systematic Raman spectroscopic study of the complexation of uranyl with fluoride.

A simple aqueous complexing system of UO22+ with F- is selected to systematically illustrate the application of Raman spectroscopy in exploring uranyl(VI) chemistry. Five successive complexes, UO2F+, UO2F2(aq), UO2F3-, UO2F42-, and UO2F53-, are identified, as well as the formation constants except for the 1 : 5 species UO2F53-, which was experimentally observed here for the first time. The standard relative molar Raman scattering intensity for each species is obtained by deconvolution of the spectra collected during titrations. The results of relativistic quantum chemical first-principles and ab initio calculations are presented for the complete set of [UO2(H2O)mFn]2-n complexes (n = 0-5), both for the gas phase as well as for aqueous solution modelling bulk water using the conductor-like screening model. Electronic structure calculations at the Møller-Plesset second-order perturbation theory level provide accurate geometrical parameters and in particular reveal that k water molecules in the second coordination sphere coordinating to the F- ligands in the resulting [UO2(H2O)mFn]2-n(H2O)k complexes need to be treated explicitly in order to obtain vibrational frequencies in very good agreement with experimental data. The thermodynamics and structural information obtained in this work and the developed methodology could be instructive for the future experimental and computational research on the complexation of the uranyl ion.

Microfluidic extensional flow device to study mass transfer dynamics in the polymer microparticle formation process.

Polymer microparticles are often used to encapsulate drugs for sustained drug-release treatments. One of the ways they are manufactured is by using a solvent extraction process, in which the polymer solution is emulsified into an aqueous bulk phase using a surfactant as a stabilizing agent, followed by the removal of the solvent. The radius of a polymer drop decreases as a function of time until the polymer reaches the gelling point, after which it is separated and dried. Among the various operating parameters, the rate of solvent extraction is a critical step that affects the morphology and porosity, and consequently, the kinetics of drug release. But a fundamental mechanistic understanding of the solvent extraction dynamics as a function of shear is still unexplored. In this study, we have developed an experimental mass transfer model to predict the extraction by using the microfluidic extensional flow device (MEFD) to probe the shear and extraction dynamics at the level of a single drop in a linear extensional flow field. We used a computer-controlled feedback algorithm to manipulate the flow field and hydrodynamically trap a Hele-Shaw drop and observe the extraction process. For the polymer solution, we used a biocompatible polymer, poly-lactic-co-glycolic acid (PLGA) with ethyl acetate (EtOAc) as the solvent. Our experiments were conducted by varying the extensional rate (G) in the channel from ∼0.1 s-1 to ∼10 s-1, and using an analytical solution of the flow field, we captured the dissolution process and measured the change in drop radius (R) with time (t). Interestingly, we initially observed a short-time asymptote R ∼ t, and later the long-time asymptote of R = constant; both trends were physically explained. The transport model developed in this work can be used to predict extraction rates and polymer microparticle composition for any polymer-solvent system. This work is also an important contribution to the literature on convective mass transfer in partially miscible emulsions.

Microdroplet assisted hollow ZnCdS@PDA nanocages' synergistic confinement effect for promoting photocatalytic H2O2 production.

Solar-driven photocatalytic H2O2 production is greatly impeded by the slow mass transfer and rapid recombination of photogenerated charge carriers for multiphase reactions. Polydopamine (PDA)-coated hollow ZnCdS (ZnCdS@PDA) octahedral cages with sulfur vacancies were constructed as micro-reactors to provide a delimited micro-environment for highly efficient paired H2O2 production through water oxidation coupled with oxygen reduction. At neutral pH, hollow ZnCdS@PDA cages exhibited a high H2O2 production yield of 45.5 mM g-1 h-1 without the assistance of sacrificial agents in bulk solution, which can be attributed to the distinguished space constraint in hollow nanocages and a surprisingly adjusted band structure. Compared to the bulk water system, H2O and O2 inside the hollow nanocage can form an ideal system for boosting such nanoconfined H2O or O2 molecules' adsorption/enrichment on the interior of the ZnCdS active sites. More importantly, the photocatalytic yield of H2O2 generation (H2O2 concentrations of 190-65.6 mM g-1 h-1) obtained in the abundant gas-liquid interface of microdroplets is dramatically higher than that obtained in an aqueous bulk environment under visible light conditions without using sacrificial agents. This enhancement can be attributed to the synergistic effect of the hollow ZnCdS@PDA nanocage reactor and the microdroplet confinement photocatalysis reaction. Particularly, the improved/confined enhancement of O2 availability and enhanced charge separation, along with high catalytic durability are the main reasons leading to significant H2O2 production due to an ultrahigh interfacial electric field and an extremely large specific surface area in microdroplets. In addition to producing a highly concentrated liquid of hydrogen peroxide during the microdroplet photoreaction, we also obtained white solid hydrogen peroxide powder with strong oxidizing properties reducing costs and increasing safety in storage and transportation. This study highlights that nano-liquid catalysis (using microdroplets) provides a very efficient pathway for accelerating semiconductor photocatalysis limited by gas diffusion in a liquid.

Lignin-Induced Click Synthesis of Au, Ag, Pd, and Iron Oxide Nanoparticles and Their Nanocomposites in Aqueous Bulk and at the Solid–Liquid Interface

Lignin-Induced Click Synthesis of Au, Ag, Pd, and Iron Oxide Nanoparticles and Their Nanocomposites in Aqueous Bulk and at the Solid–Liquid Interface

Water-Insoluble Sustainable Magnetic Nanoparticles for Green Extraction of Metallic Pollutants from Aqueous Bulk: Host–Guest Interactions at Immiscible Interfaces

Water-Insoluble Sustainable Magnetic Nanoparticles for Green Extraction of Metallic Pollutants from Aqueous Bulk: Host–Guest Interactions at Immiscible Interfaces

Spontaneous dark formation of OH radicals at the interface of aqueous atmospheric droplets.

Hydroxyl radical (OH) is a key oxidant that triggers atmospheric oxidation chemistry in both gas and aqueous phases. The current understanding of its aqueous sources is mainly based on known bulk (photo)chemical processes, uptake from gaseous OH, or related to interfacial O3 and NO3 radical-driven chemistry. Here, we present experimental evidence that OH radicals are spontaneously produced at the air-water interface of aqueous droplets in the dark and the absence of known precursors, possibly due to the strong electric field that forms at such interfaces. The measured OH production rates in atmospherically relevant droplets are comparable to or significantly higher than those from known aqueous bulk sources, especially in the dark. As aqueous droplets are ubiquitous in the troposphere, this interfacial source of OH radicals should significantly impact atmospheric multiphase oxidation chemistry, with substantial implications on air quality, climate, and health.

Influence of Hydrophobic and Hydrophilic Chain Length of CiEj Surfactants on the Solubilization of Active Pharmaceutical Ingredients.

Up to 90% of all newly developed active pharmaceutical ingredients (APIs) are poorly water soluble, most likely also showing a low oral bioavailability. In order to increase the aqueous solubility of these APIs, surfactants are promising excipients to increase both solubility and consequently bioavailability (e.g., in lipid- and surfactant-based drug delivery systems). In this work, we investigated the influence of hydrophobic and hydrophilic chain lengths of CiEj surfactants (C8E6, C10E6, and C10E8) toward the solubilization of fenofibrate, naproxen, and lidocaine. Furthermore, we investigated the partitioning of these APIs between the surfactant aggregates and the surrounding aqueous bulk phase. For all APIs considered, we determined the locus of API solubilization as well as the individual aggregation numbers (Nagg) of surfactants and API molecules in an API/surfactant aggregate. We further determined the hydrodynamic radius (Rh) of the API/surfactant aggregates in the absence and presence of the APIs. The size of the API/surfactant aggregates (Nagg, Rh) passes through a minimum upon lidocaine solubilization; it gradually increases upon naproxen solubilization and is almost constant upon fenofibrate solubilization. The results give valuable insights into the solubilization mechanisms of APIs in the CiEj surfactant aggregates. Our results reveal that fenofibrate is solely solubilized in the hydrophobic core of the CiEj surfactant aggregates, as only the hydrophobic chain length of the surfactant influences its solubilization. Naproxen is solubilized in the palisade layer of the surfactant aggregates, as both the hydrophobic and hydrophilic chain lengths are decisive for its solubilization. Lidocaine is mainly solubilized in the rather hydrophilic corona region of the surfactant aggregates, as the hydrophilic chain length of the surfactant governs its solubilization. The results further reveal that the hydrophilic/lipophilic balance is not an appropriate measure to estimate the solubilization capacity of surfactant aggregates.

Reaction Pathways for the Enzymatic Degradation of Poly(Ethylene Terephthalate): What Characterizes an Efficient PET-Hydrolase?

Bioprocessing of polyester waste has emerged as a promising tool in the quest for a cyclic plastic economy. One key step is the enzymatic breakdown of the polymer, and this entails a complicated pathway with substrates, intermediates, and products of variable size and solubility. We have elucidated this pathway for poly(ethylene terephthalate) (PET) and four enzymes. Specifically, we combined different kinetic measurements and a novel stochastic model and found that the ability to hydrolyze internal bonds in the polymer (endo-lytic activity) was a key parameter for overall enzyme performance. Endo-lytic activity promoted the release of soluble PET fragments with two or three aromatic rings, which, in turn, were broken down with remarkable efficiency (kcat /KM values of about 105 M-1 s-1 ) in the aqueous bulk. This meant that approximatly 70 % of the final, monoaromatic products were formed via soluble di- or tri-aromatic intermediates.

Spread and adsorbed layers of protein fibrils at water –air interface

The properties of adsorbed layers of protein fibrils differ significantly from the properties of fibril spread layers on an aqueous subphase. If the dependencies of the dynamic surface elasticity on surface pressure of Lysozyme (LYS) and β-lactoglobulin (BLG) aqueous dispersions proved to be close to the results for native protein solutions, LYS and BLG spread layers on the surface of 0.1 M NaCl solution exhibited the surface elasticity more than two times higher than the values for protein solutions with the same NaCl concentatration, presumably due to lower surface concentrations of hydrolysed peptides in the latter case. The properties of fibril spread and adsorbed layers and also their morphology, unlike the surface properties of protein solutions, depend noticeably on the ionic strength of the aqueous bulk phase. This dependence is stronger in case of LYS layers, which are also more prone to the formation of macroscopic and mesoscopic surface aggregates as compared with BLG layers.

Microheterogeneous Triplet Oxidation of Hydrophobic Organic Contaminants in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

Dissolved black carbon (DBC) is proven to accelerate the triplet-mediated photodegradation of hydrophobic organic contaminants (HOCs). However, its photosensitization mechanisms are not clear. In this study, five HOCs including 2,4,6-trimethylphenol, N,N-dimethylaniline, 17β-estradiol, 17α-ethinylestradiol, and bisphenol A were selected as model compounds to explore the triplet-mediated phototransformation of HOCs in illuminated DBC solutions. All five HOCs presented high organic carbon-water partition coefficient (KOC) values in DBC solutions, indicating the strong sorption capacity of DBC for HOCs. When reaching sorption equilibrium, the apparent pseudo-first-order rate constants of HOCs vs log[DBC] were well fitted with a sorption-enhanced phototransformation model (R2 > 0.98). Using the sorption-enhanced phototransformation model, the degradation rates of HOCs determined at intra-DBC (kDBC,HOCs') were 1-2 orders of magnitude higher than those observed in aqueous bulk solution (kHOCsaq). Moreover, typical triplet quenchers (2,4,6-trimethylphenol and oxygen) exhibited a microheterogeneous quenching effect on the triplet-mediated photodegradation of 17β-estradiol. Therefore, our results suggested that HOCs underwent a microheterogeneous photooxidative degradation process in DBC solutions. Furthermore, a sorption-enhanced phototransformation mechanism was proposed to elucidate the microheterogeneous photooxidative behavior of HOCs in DBC solutions. This study provides new insights into the fate and transport of HOCs in aquatic environments.

Impacts of oil components on the stability of aqueous bulk CO2 foams: An experimental study

Study of foam stability in the presence of oil components is mainly devoted to the impacts of aliphatic components like short- and long-chained alkanes. In this study, several experiments, including critical micelle concentration (CMC) determination, IFT measurement, high pressure bulk foam stability as well as foam texture visualization and analysis have been designed and performed in the presence of various oil solution samples to explore the impacts of aromatic components and compare them with the impacts of aliphatic components on CO2 foam stability. Alpha-Olefin-Sulfonate (AOS) surfactant solutions with different concentrations of surfactant in the presence of various synthetic oil solutions comprising toluene and n-heptane were prepared to compare the interfacial behavior and performance of the surfactant solutions containing aromatic and aliphatic components with regards to foam stability. The results revealed that, due to higher micellar solubilization of the n-heptane as the aliphatic component compared to toluene, surfactant surface activity would be more detrimentally impacted by the presence n-heptane. Employing electrical conductivity measurements, it was observed that the CMC of surfactant solutions with addition of 1 vol% of toluene and n-heptane to the surfactant solution, increased by 15 and 19 times, respectively. Increase in surfactant concentration in solutions above CMC with no oil compound, did not show any promising improvement on foam stability. However, in the presence of different oil additives, increase in surfactant concentration from 0.1 wt% to 0.5 wt% resulted in the increase in foam stability by 45% on average measured by foam half-life time where the foam was generated by aeration method. This observation was further validated by the decrease in IFT, measured by spinning drop method, from the average range of 1.4 mN/m for different oil solutions to 0.6 mN/m by increasing surfactant concentration from 0.1 wt% to 0.5 wt%. IFT measurements between surfactant solutions and different oleic samples with oil components suggested that the presence of higher n-heptane in oil solutions resulted in higher IFT. Similar behavior was observed in foam stability measurements. Generally, addition of oil components to the foam solution resulted in lower foam stability. That is, higher oil content concentration would result in lower foam stability. Also, the presence of n-heptane had more detrimental impacts on foam stability compared to the presence of toluene. The texture of the resulted foam in the presence of toluene and n-heptane was visualized. It was observed that the texture of the foam generated in the presence of toluene had smaller bubble size compared to that in the presence of n-heptane. Also, it was observed that as time passes, oil droplets migrate from lamellae to the plateau borders, resulting in lamellae thinning and foam bubble coarsening and rupture.

Water/transcutol/lecithin/M−812 green cationic nanoemulsion to treat oxytetracycline contaminated aqueous bulk solution

Oxytetracycline (OXT) has been recognized as the most common veterinary medicine discharge responsible to cause water contamination and subsequent health issues in aquatic animals and human health. The study addressed the use of cationic (water/transcutol/lecithin/M−812) green nanoemulsion as an efficient, effective, and cost effective approach. Components were selected based on the drug solubility and HSP (Hansen solubility parameter) software (HSPiP software). Several batches of green cationic nanoemulsions (GNE1-GNE5) were tailored using medium chain triglyceride, transcutol, and lecithin as dictated in pseudoternary phase diagrams followed by thermodynamic stability study. These were characterized for globular size and size distribution, zeta potential, refractive index (RI), viscosity, and pH. Moreover, removal efficiency (%) and the impact of exposure time (5, 10, and 20 min) on removal efficiency were investigated. Finally, the treated water was assessed to ensure free from OXT using SEM-EDX (scanning electron microscopy- energy dispersive X-ray analysis mode) and ICP-OES (inductively coupled plasma-optical emission spectrometry). Result showed that removal efficiency was significantly dependent upon (a) globular size, (b) water content, (c) oil content, and (d) viscosity. However, the exposure time for emulsification had no considerable impact. The most optimized cationic GNE5 was characterized with low size (38 nm), optimal zeta potential (+26 mV), low viscosity (316.5 cP), and the highest removal efficiency (90.3% at 20 min) as compared to respective anionic nanoemulsion. SEM-EDX and ICP-OES results corroborated the absence of OXT in the treated water. Hence, this approach is promising to decontaminate anionic OXT present in wastewater using cationic GNE5 (to get OXT loaded ONE5 after dispersion).

Hemolytic Response of Iron Oxide Magnetic Nanoparticles at the Interface and in Bulk: Extraction of Blood Cells by Magnetic Nanoparticles.

Surface-active and water-soluble magnetic nanoparticles (NPs) were synthesized in the presence of a series of amphiphilic molecules of different functional groups to determine the hemolytic response and their ability to extract blood cells across the interface and aqueous bulk while maintaining minimum hemolysis. Amphiphilic molecules such as Gemini surfactants of strong hydrophobicity and low hydrophilic-lipophilic balance produced surface-active magnetic NPs, which were highly cytotoxic even when placed at the blood suspension (aqueous)-air interface. A similar behavior was shown by water-soluble magnetic NPs produced using monomeric ionic and nonionic surfactants and different amino acids. The NPs produced using mild biological surfactants and mono- and oligosaccharides of the same functional group proved to be excellent blood cell extractors with minimum hemolysis. α/β-cyclodextrin and dextrose-stabilized magnetic NPs induced negligible hemolysis and extracted more than 50% of blood cells. The results showed that nontoxic magnetic NPs are excellent blood cell extractors from the blood suspension when tagged with amphiphilic molecules possessing good biocompatibility with cell membranes without inducing hemolysis. The work highlights the biological applicability of nontoxic magnetic NPs at biointerfaces and in blood suspensions.

Mutational widening of constrictions in a formate–nitrite/H+ transporter enables aquaporin-like water permeability and proton conductance

The unrelated protein families of the microbial formate–nitrite transporters (FNTs) and aquaporins (AQP) likely adapted the same protein fold through convergent evolution. FNTs facilitate weak acid anion/H+ cotransport, whereas AQP water channels strictly exclude charged substrates including protons. The FNT channel–like transduction pathway bears two lipophilic constriction sites that sandwich a highly conserved histidine residue. Because of lacking experiments, the function of these constrictions is unclear, and the protonation status of the central histidine during substrate transport remains a matter of debate. Here, we introduced constriction-widening mutations into the prototypical FNT from Escherichia coli, FocA, and assayed formate/H+ transport properties, water/solute permeability, and proton conductance. We found that enlargement of these constrictions concomitantly decreased formate/formic acid transport. In contrast to wildtype FocA, the mutants were unable to make use of a transmembrane proton gradient as a driving force. A construct in which both constrictions were eliminated exhibited water permeability, similar to AQPs, although accompanied by a proton conductance. Our data indicate that the lipophilic constrictions mainly act as barriers to isolate the central histidine from the aqueous bulk preventing protonation via proton wires. These results are supportive of an FNT transport model in which the central histidine is uncharged, and weak acid substrate anion protonation occurs in the vestibule regions of the transporter before passing the constrictions.

Extraction of Bionanomaterials from the Aqueous Bulk by Using Surface Active and Water-Soluble Magnetic Nanoparticles.

Surface active and water-soluble magnetic nanoparticles (NPs) were used to demonstrate the extraction of bionanomaterials from the aqueous bulk. Au NPs conjugated with different water-insoluble and water-soluble proteins were used as model bionanomaterials. UV-visible studies, zeta potential, and microscopic analyses were performed to quantify the extraction. Sodium dodecyl sulfate and dimethylene bis(dodecyldimethylammonium bromide) (12-2-12) stabilized surface active magnetic NPs were fully capable of extracting Au NPs conjugated with predominantly hydrophobic proteins from the aqueous bulk when placed at the aqueous-air interface. However, they were poor in extracting Au NPs from the aqueous bulk which were coated with predominantly hydrophilic water-soluble protein. On the other hand, water-soluble dodecyldimethyl-3-ammonio-1-propanesulfonate stabilized magnetic NPs proved to be fully capable of extracting all kinds of Au NPs conjugated with either water-soluble or water-insoluble proteins. The results highlight the remarkable ability of magnetic NPs in the extraction of bionanomaterials when placed at either biointerfaces or in the aqueous bulk of biological systems.