Adsorptive removal of heavy metals from aqueous solutions: Progress of adsorbents development and their effectiveness.

Increased levels of heavy metals (HMs) in aquatic environments poses serious health and ecological concerns. Hence, several approaches have been proposed to eliminate/reduce the levels of HMs before the discharge/reuse of HMs-contaminated waters. Adsorption is one of the most attractive processes for water decontamination; however, the efficiency of this process greatly depends on the choice of adsorbent. Therefore, the key aim of this article is to review the progress in the development and application of different classes of conventional and emerging adsorbents for the abatement of HMs from contaminated waters. Adsorbents that are based on activated carbon, natural materials, microbial, clay minerals, layered double hydroxides (LDHs), nano-zerovalent iron (nZVI), graphene, carbon nanotubes (CNTs), metal organic frameworks (MOFs), and zeolitic imidazolate frameworks (ZIFs) are critically reviewed, with more emphasis on the last four adsorbents and their nanocomposites since they have the potential to significantly boost the HMs removal efficiency from contaminated waters. Furthermore, the optimal process conditions to achieve efficient performance are discussed. Additionally, adsorption isotherm, kinetics, thermodynamics, mechanisms, and effects of varying adsorption process parameters have been introduced. Moreover, heavy metal removal driven by other processes such as oxidation, reduction, and precipitation that might concurrently occur in parallel with adsorption have been reviewed. The application of adsorption for the treatment of real wastewater has been also reviewed. Finally, challenges, limitations and potential areas for improvements in the adsorptive removal of HMs from contaminated waters are identified and discussed. Thus, this article serves as a comprehensive reference for the recent developments in the field of adsorptive removal of heavy metals from wastewater. The proposed future research work at the end of this review could help in addressing some of the key limitations facing this technology, and create a platform for boosting the efficiency of the adsorptive removal of heavy metals.

Adsorptive removal of organic pollutants from aqueous solutions using novel GO/bentonite/MgFeAl-LTH nanocomposite.

The contamination of water with organic pollutants such as dyes and phenols is a serious environmental problem, requiring effective treatment methods. In the present study, a novel nanocomposite was synthesized by intercalating graphene oxide and bentonite clay into MgFeAl-layered triple hydroxide (GO/BENT/LTH), which was characterized using different techniques. The adsorption efficacy of the GO/BENT/LTH nanocomposite was assessed via the removal of two harmful organic water pollutants, namely methyl orange (MO) and 2-nitrophenol (2NP). The obtained results revealed that the maximum adsorption capacities (qmax) of MO and 2NP reached 3106.3 and 2063.5 mg/g, respectively, demonstrating the excellent adsorption performance of the nanocomposite. Furthermore, this study examined the effects of contact time, initial MO and 2NP concentrations, pH, and temperature of the wastewater samples on the adsorptive removal of MO and 2NP by the GO/BENT/LTH nanocomposite. The pH, zeta potential, and FTIR investigations suggested the presence of more than one adsorption mechanism. Thermodynamic investigations elucidated the exothermic nature of the adsorption of MO and 2NP onto the GO/BENT/LTH nanocomposite, with MO adsorption being more sensitive to temperature change. Additionally, regeneration studies revealed a marginal loss in the MO and 2NP removal with the repetitive use of the GO/BENT/LTH nanocomposite, demonstrating its reusability. Overall, the findings of this study reveal the promise of the GO/BENT/LTH nanocomposite for effective water decontamination.

Ensemble meta machine learning for predicting the adsorption of anionic and cationic dyes from aqueous solutions using Polymer/graphene/clay/MgFeAl-LTH nanocomposite.

Adsorption is one of the most promising wastewater treatment methods due to its simplicity and efficacy at ambient temperature and pressure. However, the technical and economic feasibility of this process largely depends on the performance of the utilized adsorbents. In this study, a promising adsorbent made of polyethyleneimine, graphene oxide (GO), bentonite, and MgFeAl-layered triple hydroxide (MgFeAl-LTH) has been synthesized and characterized. The results revealed that the synthesized nanocomposite (abbreviated as PGB-LTH) possesses good porosity and crystallinity. The adsorption performance of the PGB-LTH nanocomposite towards two harmful water pollutants (i.e., methyl orange (MO) and crystal violet (CV)) was investigated, and the results revealed that the nanocomposite outperforms its parental materials (i.e., GO, bentonite, and MgFeAl-LTH). The maximum adsorption capacity (qmax) of MO and CV onto the nanocomposite could reach 1666.7 and 1250.0 mg/g, respectively, as predicted using the Langmuir adsorption isotherm. Additionally, the PGB-LTH nanocomposite is highly reusable with an insignificant decline in performance upon repetitive use. In terms of thermodynamics, MO adsorption onto the nanocomposite is exothermic while CV adsorption is endothermic despite that both dyes adsorb spontaneously as revealed by the negative values of the Gibbs free energy change at all the examined temperatures. The generated adsorption data were utilized for constructing and assessing ensemble meta-machine learning techniques aimed at cost-effective simulation and prediction of the proposed adsorption method. Bagging and boosting methods were developed and evaluated intensively using the obtained adsorption data. The Extra Trees model achieved promising results as evidenced by the high correlation coefficient of 99% as well as low computed RMSE and MAE errors of 11.42 and 5.11, respectively, during the testing phase. These results demonstrate the model strong capability to effectively simulate and predict the adsorption process in question.

Experimental Investigation of Using Manganese Monoxide as a Hydrogen Sulfide Scavenger for Aqueous Drilling Fluids.

One of the most serious safety and health concerns during drilling oil and gas wells is the potential release of hydrogen sulfide (H2S) to the surface, exposing workers to high risks. Serious corrosion-related damage to handling equipment is also inevitable in the presence of H2S. Various H2S scavengers have been utilized, but each has its pros and cons; hence, research is continuing to develop an optimum and feasible scavenger. Since manganese monoxide (MnO) is a reactive metal oxide with high oxidation and absorption capabilities, it may have the potential to effectively scavenge H2S during drilling operations when included in drilling mud formulations. Consequently, the key aim of this work is to investigate the H2S scavenging performance of the aqueous drilling fluid containing MnO. This work studied the impact of MnO addition on the drilling mud's alkalinity, rheological behavior, filtration performance, and corrosion tendency. The experiments were also conducted for mud without a scavenger and a fluid containing the SourScav commercial scavenger, which serves as a benchmarking reference. The findings demonstrated that MnO performed exceptionally well for H2S scavenging where it boosted the aqueous mud's scavenging capacity from 84.3 to 426.2 mg of H2S/L of mud, showing more than 400% improvement relative to the base mud. Additionally, this scavenging performance is about 2.1 times higher than that of the commercial scavenger. As opposed to SourScav, MnO maintained the mud's pH at a safe level above 10. The addition of either MnO or SourScav did not weaken the mud rheology and provided practically satisfactory rheological parameters. Both SourScav and MnO marginally increased the formed filter-cake thickness from 2.9 to 3.9 mm with a slight increment in the filtrated volume but still within the acceptable limits. The corrosion test indicated the noncorrosive characteristics (i.e., the corrosion rate was nearly zero) of MnO and the commercial scavenger. This study illustrates the promising utilization of MnO as a cost-effective H2S scavenger, enhancing the efficiency and safety of drilling operations.

An Up-to-Date Review on the Remediation of Dyes and Phenolic Compounds from Wastewaters Using Enzymes Immobilized on Emerging and Nanostructured Materials: Promises and Challenges.

Addressing the critical issue of water pollution, this review article emphasizes the need to remove hazardous dyes and phenolic compounds from wastewater. These pollutants pose severe risks due to their toxic, mutagenic, and carcinogenic properties. The study explores various techniques for the remediation of organic contaminants from wastewater, including an enzymatic approach. A significant challenge in enzymatic wastewater treatment is the loss of enzyme activity and difficulty in recovery post-treatment. To mitigate these issues, this review examines the strategy of immobilizing enzymes on newly developed nanostructured materials like graphene, carbon nanotubes (CNTs), and metal-organic frameworks (MOFs). These materials offer high surface areas, excellent porosity, and ample anchoring sites for effective enzyme immobilization. The review evaluates recent research on enzyme immobilization on these supports and their applications in biocatalytic nanoparticles. It also analyzes the impact of operational factors (e.g., time, pH, and temperature) on dye and phenolic compound removal from wastewater using these enzymes. Despite promising outcomes, this review acknowledges the challenges for large-scale implementation and offers recommendations for future research to tackle these obstacles. This review concludes by suggesting that enzyme immobilization on these emerging materials could present a sustainable, environmentally friendly solution to the escalating water pollution crisis.

Aqueous Pb(II) Removal Using ZIF-60: Adsorption Studies, Response Surface Methodology and Machine Learning Predictions.

Zeolitic imidazolate frameworks (ZIFs) are increasingly gaining attention in many application fields due to their outstanding porosity and thermal stability, among other exceptional characteristics. However, in the domain of water purification via adsorption, scientists have mainly focused on ZIF-8 and, to a lesser extent, ZIF-67. The performance of other ZIFs as water decontaminants is yet to be explored. Hence, this study applied ZIF-60 for the removal of lead from aqueous solutions; this is the first time ZIF-60 has been used in any water treatment adsorption study. The synthesized ZIF-60 was subjected to characterization using FTIR, XRD and TGA. A multivariate approach was used to investigate the effect of adsorption parameters on lead removal and the findings revealed that ZIF-60 dose and lead concentration are the most significant factors affecting the response (i.e., lead removal efficiency). Further, response surface methodology-based regression models were generated. To further explore the adsorption performance of ZIF-60 in removing lead from contaminated water samples, adsorption kinetics, isotherm and thermodynamic investigations were conducted. The findings revealed that the obtained data were well-fitted by the Avrami and pseudo-first-order kinetic models, suggesting that the process is complex. The maximum adsorption capacity (qmax) was predicted to be 1905 mg/g. Thermodynamic studies revealed an endothermic and spontaneous adsorption process. Finally, the experimental data were aggregated and used for machine learning predictions using several algorithms. The model generated by the random forest algorithm proved to be the most effective on the basis of its significant correlation coefficient and minimal root mean square error (RMSE).

Improvement of Hydrogen Sulfide Scavenging via the Addition of Monoethanolamine to Water-Based Drilling Fluids.

The release of the lethal hydrogen sulfide (H2S) gas during the drilling of sour subterranean formations is of huge health and safety concern. Additionally, the contact of this corrosive gas with handling equipment might result in severe damages and significant economic losses. Accordingly, effective in situ scavenging of H2S while drilling is very crucial. Thus, we report herein the addition of monoethanolamine (MEA) to water-based mud with the objective of improving the H2S-scavenging efficacy of the mud. The H2S-scavenging capacity was evaluated for the MEA-containing mud and compared with the base mud and fluids containing the commercial scavengers, SourScav and triazine. Also, the key mud characteristics including rheology, filtration properties, alkalinity, and corrosion rate were investigated in the presence and the absence of MEA, and the obtained results were compared to those of SourScav and triazine. The obtained experimental results revealed that the addition of MEA to the base mud significantly improved the H2S adsorption capacity of the base mud by 117%, compared to 50 and 74% with the SourScav and triazine. Additionally, the pH value of the MEA-containing mud complied with the practical recommendations for drilling in a sour environment. Moreover, the plastic viscosity was increased by 13% to 37 cP with the MEA-containing mud with an insignificant impact on the yield point. Furthermore, the MEA-containing mud showed a favorable zero corrosion rate, as was the case for SourScav and triazine muds. However, unlike SourScav and triazine, MEA did not substantially enhance the filtration performance. Nonetheless, the filtration characteristics of the MEA-containing mud were still better than the base mud and within the recommended practical range for water-based muds. Overall, the results presented in this study reveal that the addition of monoethanolamine to water-based muds improves the mud characteristics and, more importantly, provides a superior H2S-scavenging performance relative to SourScav and triazine scavengers, suggesting the commercial relevance of MEA for drilling applications.

Characteristics and pH-Responsiveness of SDBS-Stabilized Crude Oil/Water Nanoemulsions.

Nanoemulsions are colloidal systems with a wide spectrum of applications in several industrial fields. In this study, crude oil-in-water (O/W) nanoemulsions were formulated using different dosages of the anionic sodium dodecylbenzenesulfonate (SDBS) surfactant. The formulated nanoemulsions were characterized in terms of emulsion droplet size, zeta potential, and interfacial tension (IFT). Additionally, the rheological behavior, long-term stability, and on-demand breakdown of the nanoemulsions via a pH-responsive mechanism were evaluated. The obtained results revealed the formation of as low as 63.5 nm average droplet size with a narrow distribution (33-142 nm). Additionally, highly negative zeta potential (i.e., -62.2 mV) and reasonably low IFT (0.45 mN/m) were obtained at 4% SDBS. The flow-ability of the nanoemulsions was also investigated and the obtained results revealed an increase in the nanoemulsion viscosity with increasing the emulsifier content. Nonetheless, even at the highest SDBS dosage of 4%, the nanoemulsion viscosity at ambient conditions never exceeded 2.5 mPa·s. A significant reduction in viscosity was obtained with increasing the nanoemulsion temperature. The formulated nanoemulsions displayed extreme stability with no demulsification signs irrespective of the emulsifier dosage even after one-month shelf-life. Another interesting and, yet, surprising observation reported herein is the pH-induced demulsification despite SDBS not possessing a pH-responsive character. This behavior enabled the on-demand breakdown of the nanoemulsions by simply altering their pH via the addition of HCl or NaOH; a complete and quick oil separation can be achieved using this simple and cheap demulsification method. The obtained results reveal the potential utilization of the formulated nanoemulsions in oilfield-related applications such as enhanced oil recovery (EOR), well stimulation and remediation, well-bore cleaning, and formation fracturing.

Single Atom Catalysts: An Overview of the Coordination and Interactions with Metallic Supports.

Catalyst utilization is a key economic factor in heterogeneous catalysis, particularly, when noble metals are used as the active phase. A huge saving on catalyst cost can be achieved with developing a single atomic layer of the active catalyst on a given cheap support. Besides the economic benefit, single atom catalysts (SACs) have also shown superior activity and selectivity relative to catalytic particles or nanoparticles; yet they are prone to aggregation and deactivation. The development of effective, stable, and commercially viable SACs is still a huge challenge. One of the remaining key obstacles is the ability to easily and effectively tune SACs-support interactions and coordination in a way that enables the production of robust, stable, and versatile SACs. Accordingly, the coordination and interactions between metallic supports and SACs and their impacts on SACs stability and activity are reviewed in this article.

Strategies to Enhance ZnO Photocatalyst's Performance for Water Treatment: A Comprehensive Review.

Despite the photocatalytic organic pollutant degradation using ZnO started in 1910-1911, many challenges are still ahead, and several critical issues have to be addressed. Large band gap, and short life-time of photogenerated electrons and holes are critical issues negatively affect the photocatalytic activity of ZnO. Various approaches have been introduced to overcome these issues including intrinsic doping, extrinsic doping, and heterostructure. This review introduces unique and deep insights into tuning of the photocatalytic activity of ZnO. It starts by description of how to tune the photocatalytic activity of pristine ZnO through tuning its morphology, surface area, exposed face, and intrinsic defects. Afterward, the review explains how the Z-scheme approach succeed to address the redox weakened issue of heterojunction approach. In general, this review provides a clear image that helps the researcher to tune the photocatalytic activity of pristine ZnO and its heterostructure.

Optimum Selection of H2S Scavenger in Light-Weight and Heavy-Weight Water-Based Drilling Fluids.

During hydrocarbon drilling operations, the presence of hydrogen sulfide (H2S) gas could cause serious health and safety issues. Scavenging this gas and eliminating its impact are essential requirements for a safe drilling operation. This study investigated the impact of three H2S scavenger additives (copper nitrate, iron gluconate, and potassium permanganate) on water-based drilling fluids (WBDFs). The additives were tested on two actual field drilling mud samples that differ mainly in their weight. The scavengers' impact on drilling muds was investigated by measuring their scavenging capacity and their effect on rheology, fluid loss, and pH. Potassium permanganate outperformed the other scavengers when added to the lighter (lower density) WBDF. However, it did not impact the scavenging capacity of the heavier mud system. Copper nitrate outperformed the other scavengers in the heavier drilling mud system. Also, the addition of copper nitrate in the lighter mud system increased its H2S-scavenging capacity greatly, while for iron gluconate, it did not perform very well. Overall, all the scavenger-containing drilling muds did not have any significant harmful impact on the plastic viscosity or the fluid loss properties of the drilling muds. Furthermore, all the tested drilling mud samples showed an excellent ability to clean wellbores and suspend drill cuttings evident by the high carrying capacity with the exception of iron gluconate or potassium permanganate with the heavy mud system.

Experimental Investigation of the Rheological Behavior of an Oil-Based Drilling Fluid with Rheology Modifier and Oil Wetter Additives.

Drilling issues such as shale hydration, high-temperature tolerance, torque and drag are often resolved by applying an appropriate drilling fluid formulation. Oil-based drilling fluid (OBDF) formulations are usually composed of emulsifiers, lime, brine, viscosifier, fluid loss controller and weighting agent. These additives sometimes outperform in extended exposure to high pressure high temperature (HPHT) conditions encountered in deep wells, resulting in weighting material segregation, high fluid loss, poor rheology and poor emulsion stability. In this study, two additives, oil wetter and rheology modifier were incorporated into the OBDF and their performance was investigated by conducting rheology, fluid loss, zeta potential and emulsion stability tests before and after hot rolling at 16 h and 32 h. Extending the hot rolling period beyond what is commonly used in this type of experiment is necessary to ensure the fluid's stability. It was found that HPHT hot rolling affected the properties of drilling fluids by decreasing the rheology parameters and emulsion stability with the increase in the hot rolling time to 32 h. Also, the fluid loss additive's performance degraded as rolling temperature and time increased. Adding oil wetter and rheology modifier additives resulted in a slight loss of rheological profile after 32 h and maintained flat rheology profile. The emulsion stability was slightly decreased and stayed close to the recommended value (400 V). The fluid loss was controlled by optimizing the concentration of fluid loss additive and oil wetter. The presence of oil wetter improved the carrying capacity of drilling fluids and prevented the barite sag problem. The zeta potential test confirmed that the oil wetter converted the surface of barite from water to oil and improved its dispersion in the oil.

H2S Scavenging Capacity and Rheological Properties of Water-Based Drilling Muds.

Drilling hydrocarbon formations where hydrogen sulfide (H2S) is present could lead to the carryover of H2S with the drilling mud (i.e., drilling fluid) to the surface, exposing working personnel to this lethal gas. Additionally, H2S is very corrosive, causing severe corrosion of metal parts of the drilling equipment, which in turn results in serious operational problems. The addition of an effective H2S scavenger(s) in the drilling mud formulations will overcome these health, safety, and operational issues. In this work, zinc oxide (ZnO), which is a common H2S scavenger, has been incorporated into water-based drilling mud. The H2S scavenging performance of this ZnO-containing drilling mud has been assessed. Additionally, drilling mud formulations containing either copper nitrate (Cu(NO3)2·3H2O) or potassium permanganate (KMnO4) have been prepared, and their H2S scavenging performances have been studied and compared to that of the ZnO-containing drilling mud. It has been observed that the scavenging performance (in terms of the H2S amounts scavenged up to the breakthrough time and at the saturation condition) of the ZnO-containing drilling mud is very poor compared to those of the copper nitrate-containing and KMnO4-containing drilling muds. For instance, the amounts of H2S scavenged up to the breakthrough time by ZnO-containing, copper nitrate-containing, and KMnO4-containing drilling muds were 5.5, 15.8, and 125.3 mg/g, respectively. Furthermore, the amounts of H2S scavenged at the saturation condition by these drilling muds were, respectively, 35.1, 146.8, and 307.5 mg/g, demonstrating the superiority of the KMnO4-containing drilling mud. Besides its attractive H2S scavenging performance, the KMnO4-containing drilling mud possessed more favorable rheological properties [i.e., plastic viscosity (PV), yield point (YP), carrying capacity of the drill cuttings, and gelling characteristics] relative to the base and the ZnO-containing and copper nitrate-containing drilling muds. The addition of KMnO4 to the base drilling mud increased its apparent viscosity, PV, and YP by 20, 33, and 10%, respectively. Additionally, all tested drilling muds possessed acceptable fluid loss characteristics. To the best of our knowledge, there are so far no published studies concurrently tackling the H2S scavenging (i.e., breakthrough time, breakthrough capacity, saturation time, saturation capacity, and scavenger utilization) and the rheological properties of water-based drilling muds, as demonstrated in the current study, highlighting the novelty of this work.

Enzymatic removal of protein fouling from self-assembled cellulosic nanofilms: experimental and modeling studies.

Protein fouling is a serious problem in many food, pharmaceutical and household industries. In this work, the removal of rubisco protein fouling from cellulosic surfaces using a protease (subtilisin A) has been investigated experimentally and mathematically. The cellulosic surfaces were prepared using self-assembled monolayers (SAMs) on a surface plasmon resonance biosensor (chip) surface after conjugating cellulose to α-lipoic acid. Rubisco adsorption on the prepared cellulosic SAMs was found to be irreversible, leading to the creation of a tough protein fouling. The heterogeneous enzymatic cleansing of such tough fouling involves enzyme transfer to the surface and the subsequent removal of the rubisco via protease activity. In this work, these two processes were decoupled, allowing enzyme transfer and enzymatic surface reaction to be parameterized separately. Mathematical modeling of the enzymatic cleaning of protein fouling from cellulosic SAMs revealed that enzymatic mobility at the interface is an important factor. The approach presented in this work might be useful in designing better protein fouling-resistant surfaces. It could also be used to guide efforts to screen and gauge the cleaning performance of detergent-enzyme formulations.

Dynamic surface tension and adsorption mechanism of surfactin biosurfactant at the air-water interface.

The dynamic adsorption of the anionic biosurfactant, surfactin, at the air-water interface has been investigated in this work and compared to those of two synthetic surfactants: the anionic sodium dodecylbenzenesulfonate (SDBS) and the nonionic octaethylene glycol monotetradecyl ether (C14E8). The results revealed that surfactin adsorption at the air-water interface is purely controlled by diffusion mechanism at the initial stage of the adsorption process (i.e., [Formula: see text]), but shifts towards a mixed diffusion-barrier mechanism when surface tension approaches equilibrium (i.e., [Formula: see text]) due to the development of an energy barrier for adsorption. Such energy barrier has been found to be a function of the surfactin bulk concentration (increases with increasing surfactin concentration) and it is estimated to be in the range of 1.8-9.5 kJ/mol. Interestingly, such a trend (pure diffusion-controlled mechanism at [Formula: see text] and mixed diffusion-barrier mechanism at [Formula: see text]) has been also observed for the nonionic C14E8 surfactant. Unlike the pure diffusion-controlled mechanism of the initial surfactin adsorption, which was the case in the presence and the absence of the sodium ion (Na+), SDBS showed a mixed diffusion-barrier controlled at both short and long time, with an energy barrier of 3.0-9.0 and 3.8-18.0 kJ/mol, respectively. Such finding highlights the nonionic-like adsorption mechanism of surfactin despite its negative charge.

Benchmarking the Self-Assembly of Surfactin Biosurfactant at the Liquid-Air Interface to those of Synthetic Surfactants.

The adsorption of surfactin, a lipopeptide biosurfactant, at the liquid-air interface has been investigated in this work. The maximum adsorption density and the nature and the extent of lateral interaction between the adsorbed surfactin molecules at the interface were estimated from surface tension data using the Frumkin model. The quantitative information obtained using the Frumkin model was also compared to those obtained using the Gibbs equation and the Langmuir-Szyszkowski model. Error analysis showed a better agreement between the experimental and the calculated values using the Frumkin model relative to the other two models. The adsorption of surfactin at the liquid-air interface was also compared to those of synthetic anionic, sodium dodecylbenzenesulphonate (SDBS), and nonionic, octaethylene glycol monotetradecyl ether (C14E8), surfactants. It has been estimated that the area occupied by a surfactin molecule at the interface is about 3- and 2.5-fold higher than those occupied by SDBS and C14E8 molecules, respectively. The interaction between the adsorbed molecules of the anionic biosurfactant (surfactin) was estimated to be attractive, unlike the mild repulsive interaction between the adsorbed SDBS molecules.

Self-assembly of a surfactin nanolayer at solid-liquid and air-liquid interfaces.

Surfactin, a sustainable and environmentally friendly surface active agent, is used as a model to study the adsorption of biosurfactants at hydrophobic and hydrophilic solid-liquid interfaces as well as the air-liquid interface. Surfactin adsorption was monitored as a function of time and concentration using surface plasmon resonance (SPR) technique in the case of the solid-liquid interfaces or the drop shape analysis (DSA) technique in the case of the air-liquid interface. The results obtained in this study showed that surfactin adsorption at the "hard" hydrophobic (functionalized with octadecanethiol) solid-liquid and the "soft" air-liquid interface were 1.12 ± 0.01 mg m(-2) (area per molecule of 157 ± 2 Å(2)) and 1.11 ± 0.05 mg m(-2) (area per molecule of 159 ± 7 Å(2)), respectively, demonstrating the negligible effect of the interface "hardness" on surfactin adsorption. The adsorption of surfactin at the hydrophilic (functionalized with ß-mercaptoethanol) solid-liquid interface was about threefold lower than its adsorption at the hydrophobic-liquid interfaces, revealing the importance of hydrophobic interaction in surfactin adsorption process. The affinity constant of surfactin for the investigated interfaces follows the following order: air > octadecanethiol > ß-mercaptoethanol. Biosurfactants, such as surfactin, are expected to replace the conventional fossil-based surfactants in several applications, and therefore the current study is a contribution towards the fundamental understanding of biosurfactant behavior, on a molecular level, at hydrophobic and hydrophilic solid-liquid interfaces in addition to the air-liquid interface. Such understanding might aid further optimization of the utilization of surfactin in a number of industrial applications such as enhanced oil recovery, bioremediation, and detergency.

Lysozyme binding to tethered bilayer lipid membranes prepared by rapid solvent exchange and vesicle fusion methods.

Tethered bilayer lipid membranes (tBLMs) are important tools for studying protein-lipid interactions. The widely used methodology for the preparation of these membranes is the fusion of phospholipid vesicles from an aqueous medium onto an anchored phospholipid layer. The preparation of phospholipid vesicles is a long and tedious procedure. There is another simple method, rapid solvent exchange, for preparing lipid membranes. However, there is a lack of information on the effects of the preparation method of tBLMs on their interactions with proteins. Therefore, we present in this paper a comparative study on the binding of lysozyme onto tBLMs prepared by the abovementioned methods. The prepared tBLMs have either zwitterionic or anionic characteristics. The results show that lysozyme binding onto the prepared tBLMs is unaffected by the preparation method of the tBLMs, suggesting that the tedious fusion method might be replaced by the simple rapid solvent exchange method without altering the level of protein-lipid interactions.

Comparison of positional surfactant isomers for displacement of rubisco protein from the air-water interface.

Protein-surfactant interaction, which is a function of the protein and surfactant characteristics, is a common phenomenon in a wide range of industrial applications. In this work, we used rubisco, the most abundant protein in nature, as a model protein and sodium dodecylbenzenesulfonate (SDOBS), one of the most widely used commercial surfactants, with two positional isomers (SDOBS-2 and SDOBS-6), as a model surfactant. We first examined the surface tension and the mechanical properties of interfacial mixed rubisco-SDOBS films adsorbed at the air-water interface. The concentration of rubisco in solution was fixed at 0.1 mg mL(-1) while the SDOBS concentration varied from 0 to 150 µM. Both the surface tension and the mechanical strength of the interfacial film decreased with increasing SDOBS concentration. Overall, the surface tension of a rubisco-SDOBS-6 mixture is lower than that of rubisco-SDOBS-2, while the mechanical strength of both systems is similar. Neutron reflection data suggest that rubisco protein is likely denatured at the interface. The populations of rubisco and SDOBS of the mixed systems at the interface were determined by combining non-deuterated and deuterated SDOBS to provide contrast variation. At a low surfactant concentration, SDOBS-6 has a stronger ability to displace rubisco from the air-water interface than SDOBS-2. However, when surfactant concentration reaches 50 µM, SDOBS-2 has a higher population than SDOBS-6, with more rubisco displaced from the interface. The results presented in this work suggest that the extent of protein displacement from the air-water interface, and hence the nature of the protein-surfactant interactions at the interface, are strongly affected by the position of surfactant isomerisation, which might allow the design of formulations for efficient removal of protein stains.

Tethering antimicrobial peptides: current status and potential challenges.

Antimicrobial peptides (AMPs) are next generation antibiotics which will make excellent coating agents for a myriad of devices because they are far less susceptible to the development of pathogen resistance compared to conventional antibiotics, exhibit rapid and broad-spectrum killing profiles, and are effective at low concentrations. These advantages, however, are compromised upon AMP tethering to solid supports. The effects of peptide-tethering strategies in governing AMP orientation, surface density, flexibility, and activity are reviewed. Understanding AMP structure-function relationship in the tethered conformation will enable rational improvements of immobilisation parameters. Foreseeable challenges in the development of AMP-coated devices such as microbial accumulation on implant surface and the lack of direct biomolecular structure and orientation data of peptides on surfaces are also discussed, and solutions to address these roadblocks are also proposed.