Influence of buffer on colloidal stability, microstructure, and rheology of cellulose nanocrystals in hyaluronic acid suspensions.

Hyaluronic acid (HA) is a natural biopolymer found in various human tissues, while cellulose nanocrystals (CNCs) extracted from pulp fibers have unique rheological properties and biocompatibility. Due to the superior biomechanical properties of CNC and HA, a CNC-based HA suspension may be useful in biomedical applications. While buffers are an essential constituent of any suspension used for biomedical applications to maintain the desired pH level, they can significantly affect the properties of the suspension, including colloidal stability, microstructure, and rheological characteristics. To our knowledge, this is the first study analyzing the influence of buffer solutions on the suspension characteristics of HA/CNC systems, integrating both theoretical and experimental approaches. The results revealed an alignment between predictions of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and results from experiments characterizing a buffer-specific trend in colloidal stability. Suspensions with a higher energy barrier showed higher colloidal stability, with a lower tendency for phase separation and agglomerate formations. The microstructural analysis of CNC tactoids in the suspension revealed the existence of the hedgehog defect when dispersed in different buffer solutions. The defect is predicted to be caused by the pH-dependent protonation and deprotonation of HA. Furthermore, steady shear viscometry showed a microstructural-dependent shear viscosity trend, which, in turn, depends on the buffer solution. The study provides novel insights into the microstructural and bulk properties of HA and CNC suspensions in various buffer solutions. The results highlight the importance of solvent choice in tailoring the properties of the suspension for specific biomedical applications. These findings may be helpful in formulating HA and CNC suspensions for different biomedical applications, including drug delivery systems and viscosupplement injections.

Comparative study of polystyrene microplastic transport behavior in three different filter media: Quartz sand, zeolite, and anthracite.

Microplastics (MPs) are emerging contaminants that are attracting increasing interest from researchers, and the safety of drinking water is greatly affected by their transportation during filtration. Polystyrene (PS) was selected as a representative MPs, and three filter media (quartz sand, zeolite, and anthracite) commonly found in water plants were used. The retention patterns of PS-MPs by various filter media under various background water quality conditions were methodically investigated with the aid of DLVO theory and colloidal filtration theory. The results show that the different structures and elemental compositions of the three filter media cause them to exhibit different surface roughnesses and surface potentials. A greater surface roughness of the filter media can provide more deposition sites for PS-MPs, and the greater surface roughness of zeolite and anthracite significantly enhances their ability to inhibit the migration of PS-MPs compared with that of quartz sand. However, surface roughness is not the only factor affecting the migration of MPs. The lower absolute value of the surface potential of anthracite causes the DLVO energy between it and PS-MPs to be significantly lower than that between zeolite and PS-MPs, which results in stronger retention of PS-MPs by anthracite, which has a lower surface roughness, than zeolite, which has a higher surface roughness. The transport of PS-MPs in the medium is affected by the combination of the surface roughness of the filter media and the DLVO energy. Under the same operating conditions, the retention efficiencies of the three filter materials for PS-MPs followed the order of quartz sand < zeolite < anthracite. Additionally, the conditions of the solution markedly influenced the transport ability of PS-MPs within the simulated filter column. The transport PS-MPs in the simulated filter column decreased with increasing solution ionic strength and cation valence. Naturally, dissolved organic matter promoted the transfer of PS-MPs in the filter layer, and humic acid had a much stronger facilitating impact than fulvic acid. The study findings might offer helpful insight for improving the ability of filter units ability to retain MPs.

Effect of Solvent Composition on Non-DLVO Forces and Oriented Attachment of Zinc Oxide Nanoparticles.

Oriented attachment (OA) occurs when nanoparticles in solution align their crystallographic axes prior to colliding and subsequently fuse into single crystals. Traditional colloidal theories such as DLVO provide a framework for evaluating OA but fail to capture key particle interactions due to the atomistic details of both the crystal structure and the interfacial solution structure. Using zinc oxide as a model system, we investigated the effect of the solvent on short-ranged and long-ranged particle interactions and the resulting OA mechanism. In situ TEM imaging showed that ZnO nanocrystals in toluene undergo long-range attraction comparable to 1kT at separations of 10 nm and 3kT near particle contact. These observations were rationalized by considering non-DLVO interactions, namely, dipole-dipole forces and torques between the polar ZnO nanocrystals. Langevin dynamics simulations showed stronger interactions in toluene compared to methanol solvents, consistent with the experimental results. Concurrently, we performed atomic force microscopy measurements using ZnO-coated probes for the short-ranged interaction. Our data are relevant to another type of non-DLVO interaction, namely, the repulsive solvation force. Specifically, the solvation force was stronger in water compared to ethanol and methanol, due to the stronger hydrogen bonding and denser packing of water molecules at the interface. Our results highlight the importance of non-DLVO forces in a general framework for understanding and predicting particle aggregation and attachment.

Surface properties of mycoparasitic Pythium species and their interaction with model materials.

Pythium oligandrum, a soil-born oomycete, is an effective biological control agent exhibiting antagonistic and parasitic activity against pathogenic fungi. This study is the first attempt to characterize its surface properties and to apply models of physicochemical interactions (thermodynamic, DLVO and XDLVO) to quantify its adhesion properties to a model material, represented by magnetic beads (MB). The predictions of interaction models were based on experimental data (contact angles, zeta potentials, size). Adhesion intensities (AI) were determined experimentally taking advantage of MB with different surface properties. The role of weak physicochemical interactions was estimated by comparing experimental AI with model predictions. The results revealed that the surface properties of the three Pythium spp. studied were very similar and fell within the range for hydrophilic microorganisms (ΔGTOT > 0) with a predominantly negative surface charge. The most reliable description of AI was obtained using the DLVO model, including Lifshitz-van der Waals and electrostatic interactions. The highest AI between Pythium spp. and all three MB was observed at pH 3, which was supported by the DLVO prediction. The greater agreement between the sphere-sphere geometric version of the DLVO model and experiment suggests that the surface protrusions of the oospores increase the efficiency of adhesion. The surface properties of the pathogenic fungi, characterized in this work, fell within the range defined by MB and therefore it can be expected that their physicochemical interactions with Pythium spp. will also be favourable.

Co-impacts of cation type and humic acid on migration of polystyrene microplastics in saturated porous media.

The aging process of microplastics (MPs) could significantly change their physical and chemical characteristics and impact their migration behavior in soil. However, the complex effects of different cations and humic acids (HA) on the migration of aged MPs through saturated media are not clear. In this research, the migration and retention of pristine/aged PSMPs (polystyrene microplastics) under combined effects of cations (Na+, Ca2+) (ionic strength = 10 mM) and HA (0, 5, 15 mg/L) were investigated and analyzed in conjunction with the two-site kinetic retention model and DLVO theory. The findings showed that the aging process accelerated PSMPs migration under all tested conditions. Aged PSMPs were less susceptible to Ca2+ than pristine PSMPs. Under Ca2+ conditions, pristine/aged PSMPs showed higher retention than under Na+ conditions in the absence of HA. Furthermore, under Na+ conditions, the migration of aged PSMPs significantly increased at higher concentrations of HA. However, under Ca2+ conditions, the migration of aged PSMPs decreased significantly at higher concentrations of HA. In higher HA conditions, HA, Ca2+, and PSMPs interact to cause larger aggregations, resulting in the sedimentation of aged PSMPs. The DLVO calculations and two-site kinetic retention models' results showed the detention of PSMPs was irreversible under higher HA conditions (15 mg/L) with Ca2+, and aged PSMPs were more susceptible to clogging. These findings may help to understand the potential risk of migration behavior of PSMPs in the soil-groundwater environment.

Flotation mechanism and performance of air/condensate bubbles for removing oil droplets in the presence of acetic acid.

Flotation technology is widely utilized to remove emulsified oil droplets from Produced water. Organic acid adsorption on the oil droplet surface affects bubble attachment, reducing oil removal efficiency. This investigation exploited the principle of similar dissolution to synthesize condensate bubbles (CB). The surface properties of oil droplets and CB and air bubbles (AB) were appraised using FTIR, zeta potential, interfacial tension, and contact angle measurements. The research also investigated the effects of acetic acids (AA) on the adhesion of oil droplets to AB and CB along with the underlying mechanism via the Extended Derjaguin-Landau-Verwey-Overbeek (EDLVO) interaction theory and the Stefan-Reynolds model of liquid film thinning, integrated with adhesion times. Flotation efficiency and kinetic dissimilarities between AB and CB were also examined. The results indicated that CB exhibits superior lipophilic hydrophobicity compared to AB, reduced induction and spreading times upon oil droplet attachment, and maximized oil removal efficiency. Furthermore, CB could mitigate the impact of AA on adhesion. The interaction barriers between CB and oil droplets were minimal, and the thinning rate of the hydration film was quicker than in AB. The conventional first-order model proved effective in fitting the AB flotation, whereas a delay constant was applied to the model of the CB flotation rate.

A study on disinfection and adhesion behaviour between bacteria and photocatalytic nanostructures by extended DLVO.

Recently, there has been a growing concern regarding the increased contamination of water by bacteria. As a result, more attention has been paid to the potential benefits of utilizing nano adsorbents and photocatalysis for water purification. In order to better manipulate the physicochemical properties, it is crucial to gain a comprehensive understanding of the molecular behaviour between nanoparticles and pathogens. This article investigates the various interactions that can occur between Fe3O4-SiO2-TiO2 (FST) nanoparticles and bacterial cells. Moreover, it explores the impact of the SiO2 mid-layer and the governing interaction in the adhesion and degradation processes. In this regard, FST nanoparticles were prepared, and their adhesion behaviour to E. coli bacterial cells was evaluated using extended DLVO (Derjaguin-Landau-Verwey-Overbeek) theory. The following results revealed that the presence of silica transformed FST into a more hydrophobic material with a positively charged surface, thereby enhancing its affinity for bacterial adsorption. Additionally, SiO2 prevented electron/hole recombination. Amongst the various interactions, Lewis acid-base interactions had the greatest influence on the total energy and lacking energy barriers led to irreversible adhesion. Moreover, the presence of an increased number of ·OH groups on the surface resulted in enhanced bactericidal properties of FST, leading to severe damage of E. coli cells through the formation of a greater number of hydrogen bonds on the bacterial surface, which is the basis of the proposed mechanism for destruction of the bacterial structure.

Humic acid-mediated transport of a typical soil passivation remediation product (chloropyromorphite) in saturated porous media.

Conversion of labile Pb species into chloropyromorphite (CPY) using phosphorus-bearing amendments was considered to be an ideal strategy in soil passivation remediation. However, the fate and transport of CPY in the soil are poorly understood. This study aims to fill the knowledge gap by evaluating the fate and transport of CPY under environmentally relevant conditions of humic acid (HA), pH, electrolyte concentration, and species through the saturated sandy medium. Results showed that bare CPY colloids are basically immobile in sandy porous media while the co-existence of HA made the transport of CPY improved by 30%-93.5%. Facilitated transport of CPY was attributed to the increased stability of CPY and the repulsive interaction between CPY particles and sands due to HA adsorption. The mobility of CPY was also increased with increasing pH from 5.0 to 9.0. When the pH was 9 with a 10 mmol/L NaCl background solution, the stronger energy barrier between CPY and sand led to enhanced transport behavior. The divalent Ca2+ had a more dramatic effect than monovalent Na+ on the aggregation and sedimentation of CPY colloids due to its effectivescreening of the surface charge of CPY and bridging interaction with CPY particles. Derjaguin-Landau-Verwey-Overbeek theory and attachment efficiency calculation indicated that high energy barriers were responsible for the high mobility of CPY colloids, while the retention of CPY in sands was mainly caused by secondary energy minimum and physically straining. The findings of this work can help to evaluate the fate of soil passivation remediation products in natural water and soil.

Revealing the contradiction between DLVO/XDLVO theory and membrane fouling propensity for oil-in-water emulsion separation.

Oil fouling is the crucial issue for the separation of oil-in-water emulsion by membrane technology. The latest research found that the membrane fouling rate was opposite to the widely used theoretical prediction by Derjaguin-Landau-Verwey-Overbeek (DLVO) or extended DLVO (XDLVO) theory. To interpret the contradiction, the molecular dynamics was adopted to explore the molecular behavior of oil and emulsifier (Tween 80) at membrane interface with the assistance of DLVO/XDLVO theory and membrane fouling models. The decreased flux attenuation and fitting of fouling models proved that the existence of Tween 80 effectively alleviated membrane fouling. Conversely, DLVO/XDLVO theory predicted that the membrane fouling should be exacerbated with the increase of Tween 80 concentration in O/W emulsion. This contradiction originated from the different interaction energy between oil/Tween 80 molecules and polyether sulfone (PES) membrane. The favorable free energy of Tween 80 was resulted from the sulfuryl groups in PES and hydrogen bonds (O-H…O) formation further strengthened the interaction. Therefore, Tween 80 could preferentially adsorb on membrane surface and form an isolation layer by demulsification and steric hindrance and resist the aggregation of oil, which effectively alleviated membrane fouling. This study provided a new insight in the interpretation of interaction in O/W emulsion.

Adsorption of Pb(II) by UV-aged microplastics and cotransport in homogeneous and heterogeneous porous media.

To investigate the adsorption effects of aged microplastics (MPs) on Pb(II) and their co-transport properties in homogeneous (quartz sand) and heterogeneous (quartz sand with apple branches biochar) porous media, we explored the co-transport of UV-irradiated aged MPs and coexisting Pb(II) along with their interaction mechanisms. The UV aging process increased the binding sites and electronegativity of the aged MPs' surface, enhancing its adsorption capacity for Pb(II). Aged MPs significantly improved Pb(II) transport through homogeneous media, while Pb(II) hindered the transport of aged MPs by reducing electrostatic repulsion between these particles and the quartz sand. When biochar, with its loose and porous structure, was used as a porous medium, it effectively inhibited the transport capacity of both contaminants. In addition, since the aged MPs cannot penetrate the column, a portion of Pb(II) adsorbed by the aged MPs will be co-deposited with the aged MPs, hindering Pb(II) transport to a greater extent. The transport experiments were simulated and interpreted using two-point kinetic modeling and the DLVO theory. The study results elucidate disparities in the capacity of MPs and aged MPs to transport Pb(II), underscoring the potential of biochar application as an effective strategy to impede the dispersion of composite environmental pollutants.

Effect of NaNO3, NH4Cl and urea on the fate and transformation of various typical microplastics in porous media.

Understanding the transport behaviors of microplastics (MPs) in porous media is crucial in controlling MPs pollution. Given nitrogen is one of the most important nutrients in soil and groundwater systems, unclearness of the transport behaviors of microplastics (MPs) under various nitrogen conditions may inhibit the acknowledgment of MPs fate. For this reason, this study innovatively investigates the transport characteristics of four kinds of typical MPs (PVC MPs, PMMA MPs, PET MPs, and PP MPs) under various NaNO3, NH4Cl and urea conditions via column experiments numerical models. The FTIR and XPS analysis were conducted to excavate the transform of MPs. The MPs mobility was generally reduced with the increasing nitrogen concentrations. The polarity and density properties of different MPs played combined roles in transport under similar conditions. Compared to NO3-, NH4+ may neutralize the negative charge of MPs and then restrain their transport in porous media. Urea may coat the surface of MPs and promote the mobility, however, increasing concentrations of urea may result in the interattraction between MPs and porous media via hydrogen-bond and π-π interaction. PET MPs and PP MPs showed barely transform during transport under the tested conditions. Particularly, the chlorines on PVC MPs could react with the amide on urea and produce amidogen, which may improve PVC MPs transport. The N-H and C-N bond also generated on PMMA MPs in presence of urea also may enhance the mobility.

Investigating the transport and colloidal behavior of Fe3O4 nanoparticles in aqueous and porous media under varying solution chemistry parameters.

The possible adverse effects of engineered iron oxide nanoparticles, especially magnetite (Fe3O4 NP), on human health and the environment, have raised concerns about their transport and behavior in soil and water systems. Accumulating these NPs in the environment can substantially affect soil and water quality and the well-being of aquatic and terrestrial organisms. Therefore, it is essential to examine the factors that affect Fe3O4 NP transportation and behavior in soil and water systems to determine their possible environmental fate. In this work, experiments were conducted in aqueous and porous media using an environmentally relevant range of pH (5, 7, 9), ionic strength (IS) (10, 50, 100 mM), and humic acid (HA) (0.1, 1, 10 mg L-1) concentrations. Fe3O4 NPs exhibited severe colloidal instability at pH 7 (⁓ = pHPZC) and showed an improvement in apparent colloidal stability at pH 5 and 9 in aquatic and terrestrial environments. HA in the background solutions promoted the overall transport of Fe3O4 NPs by enhancing the colloidal stability. The increased ionic strength in aqueous media hindered the transport by electron double-layer compression and electrostatic repulsion; however, in porous media, the transport was hindered by ionic compression. Furthermore, the transport behavior of Fe3O4 NPs was investigated in different natural waters such as rivers, lakes, taps, and groundwater. The interaction energy pattern in aquatic systems was estimated using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. This study showed the effects of various physical-chemical conditions on Fe3O4 NP transport in aqueous and porous (sand) media.

Dewatering behavior and regulation mechanism of montmorillonite nanosheet in aqueous solution.

Two-dimensional montmorillonite nanosheet (MMTNS) is desirable building block for fabricating multifunctional materials as due to its extraordinary properties. In practical applications, however, the concentration of MMTNS prepared by exfoliation is normally too low to be used for material assembling. The general thermal-concentration method is effective, however, it can be time-consuming and require a lot of energy. In this case, the remarkable dispersion stability of MMTNS is worth noting. Herein, the extraordinary dispersion stability of MMTNS derived from electrostatic and hydration repulsion was firstly revealed by molecular dynamics (MD) simulation, which caused the poor dewatering of MMTNS. Further, based on the surface and structural chemistry of MMTNS, a series of strategies, involving charge and cross-linked structure regulation on the edge surface, as well as electrical double-layer modulation and calcification modification based on the electrolytes, were proposed to inhibit the dispersion and enhance the aggregation of MMTNS. Intriguingly, a novel chemical, Tetraethylenepentamine (TEPA) was applied in the dewatering of MMTNS. The TEPA not only act as a cross-linker to bond with MMTNS into an easy-to-dewatering 3D network structure, but also act as a switch for effortless viscosity tuning. Meanwhile, the dual function of electrolytes for electrical double layer compression and calcification modification of MMTNS was investigated by DLVO theory and structural analyses. This work offers explicit directions for improving the dewatering performance of MMTNS to meet the requirements of practical implementation.

Effects of Cr(VI) oxyanion, humic acid and solution chemistry on the aggregation and colloidal stability of green synthesized chlorapatite nanoparticles.

Aggregation is a crucial process determining the fate, mobility and ecological risks of nanomaterials. Chlorapatite nanoparticles (nClAP) exhibit widely applications in environmental remediation and consequently will inevitably enter aquatic systems. However, the aggregation characteristics of nClAP are still mostly uncovered. This study investigated the aggregation kinetics and colloidal stability of nClAP as a function of pH, humic acid (HA), Cr(VI) oxyanions, monovalent and divalent electrolytes. Results showed that pH values from 5 to 9 had a notable impact on the aqueous behaviors of nClAP. The addition of HA made the zeta potential (ZP) of nClAP more negative and thus enhanced nClAP stability through electrostatic and steric effects. Similarly, the adsorption of Cr(VI) on the surface of nClAP created a physical barrier and negative charge, improving the stability of nClAP by inducing steric force. Lower ZP and hydrodynamic diameter (HDD) reflected that the enhanced stability of nClAP by HA was more significant than Cr(VI). In comparison, the presence of Ca2+ ions were more effective than monovalent Na + ions in promoting the aggregation of nClAP. The classical DLVO theory incorporating the steric repulsion were used to interpret the aggregation and dispersion of nClAP, making it was easier to overcome energy barriers and agglomerate. This study provides new mechanistic insights which could help better understand the effects of Cr(VI) oxyanions and HA on nClAP's colloidal stability.

Goldilocks Energy Minimum: Peptide-Based Reversible Aggregation and Biosensing.

Colorimetric biosensors based on gold nanoparticle (AuNP) aggregation are often challenged by matrix interference in biofluids, poor specificity, and limited utility with clinical samples. Here, we propose a peptide-driven nanoscale disassembly approach, where AuNP aggregates induced by electrostatic attractions are dissociated in response to proteolytic cleavage. Initially, citrate-coated AuNPs were assembled via a short cationic peptide (RRK) and characterized by experiments and simulations. The dissociation peptides were then used to reversibly dissociate the AuNP aggregates as a function of target protease detection, i.e., main protease (Mpro), a biomarker for severe acute respiratory syndrome coronavirus 2. The dissociation propensity depends on peptide length, hydrophilicity, charge, and ligand architecture. Finally, our dissociation strategy provides a rapid and distinct optical signal through Mpro cleavage with a detection limit of 12.3 nM in saliva. Our dissociation peptide effectively dissociates plasmonic assemblies in diverse matrices including 100% human saliva, urine, plasma, and seawater, as well as other types of plasmonic nanoparticles such as silver. Our peptide-enabled dissociation platform provides a simple, matrix-insensitive, and versatile method for protease sensing.

Pickering phase change slurries.

HYPOTHESIS: Phase change slurries (PCS) have emerged as a promising class of oil-in-water emulsions for energy applications, but stability remains an issue. Pickering phase change slurries (PPCS) stabilized solely by nanoparticles could offer enhanced stability. We hypothesize that stability in PPCS can be achieved by tuning environmental variables of salinity and temperature. EXPERIMENTS: A paraffin-based PPCS stabilized using fumed silica nanoparticles was developed and assessed under varying NaCl concentrations (up to 150 mM) and temperatures (up to 70 °C). Extended-DLVO modeling, confocal, and cryogenic electron microscopy analyzed the silica-paraffin interactions. Rheological experiments examined the impact of effective volume fraction, thermal expansion, and salinity on the viscosity and shear stability of PPCS. The stability of the resulting formulation was assessed under high pressure and temperature conditions. FINDINGS: Increased salinity did not change the packing density of the silica at the oil-water interface (82% ± 6%) but did increase the adsorbed layer thickness and network formation, enhancing the formulation's resistance to shear-induced instability. A critical volume fraction of 0.51 ± 0.01 was identified, beyond which viscosity increased significantly. The resulting formulations remained stable under high pressures and temperatures, regardless of salinity. These findings offer insights into the variables affecting PPCS properties, assisting in designing stable PPCS formulations for diverse applications.

Predicting Outcomes of Nanoparticle Attachment by Connecting Atomistic, Interfacial, Particle, and Aggregate Scales.

Predicting nanoparticle aggregation and attachment phenomena requires a rigorous understanding of the interplay among crystal structure, particle morphology, surface chemistry, solution conditions, and interparticle forces, yet no comprehensive picture exists. We used an integrated suite of experimental, theoretical, and simulation methods to resolve the effect of solution pH on the aggregation of boehmite nanoplatelets, a case study with important implications for the environmental management of legacy nuclear waste. Real-time observations showed that the particles attach preferentially along the (010) planes at pH 8.5 and the (101) planes at pH 11. To rationalize these results, we established the connection between key physicochemical phenomena across the relevant length scales. Starting from molecular-scale simulations of surface hydroxyl reactivity, we developed an interfacial-scale model of the corresponding electrostatic potentials, with subsequent particle-scale calculations of the resulting driving forces allowing successful prediction of the attachment modes. Finally, we scaled these phenomena to understand the collective structure at the aggregate-scale. Our results indicate that facet-specific differences in surface chemistry produce heterogeneous surface charge distributions that are coupled to particle anisotropy and shape-dependent hydrodynamic forces, to play a key role in controlling aggregation behavior.

Metal Ion-induced Gelation of High-concentration Graphite-like Crystalline Nanosheet Aqueous Suspensions.

The stability and transformation of nanomaterial aqueous suspensions are essential for their applications. Preparation of high-concentration carbon nanomaterials suspensions remains challenging due to their nonpolar nature. Herein, 200 mg mL-1 carbon nanomaterial aqueous suspensions are achieved by using graphite-like crystalline nanosheets (GCNs) with high hydrophilicity. Furthermore, these high-concentration GCN aqueous suspensions spontaneously transform into gels when induced by mono-, di-, and trivalent metal salt electrolytes at room temperature. Theoretical calculation of potential energy by DLVO theory reveals that the gelatinized GCNs is a new and metastable state between two usual forms of solution and coagulation. It is shown that the gelation of GCNs is due to the preferential orientation of nanosheets in an edge-edge arrangement, which differs from the case of solution and coagulation. High-temperature treatment of GCN gels produces metal/carbon materials with pore structures. This work provides a promising opportunity to create various metal/carbon functional materials.

Experimental measurements and numerical simulations of the transport and retention of nanocrystal CdSe/ZnS quantum dots in saturated porous media: Effects of electrolytes, organic ligand, and natural organic matter.

This study explores the transport and retention of CdSe/ZnS quantum dot (QD) nanoparticles in water-saturated sand columns as a function of electrolytes (Na+ and Ca2+), ionic strength, organic ligand citrate, and Suwannee River natural organic matter (SRNOM). Numerical simulations were carried out to understand the mechanisms that govern the transport and interactions of QDs in porous media and to assess how environmental parameters impact these mechanisms. An increase in the ionic strength of NaCl and CaCl2 increased QDs retention in porous media. The reduction of the electrostatic interactions screened by dissolved electrolyte ions and the increase of divalent bridging effect are the causes for this enhanced retention behavior. Citrate or SRNOM enhanced QDs transport in NaCl and CaCl2 systems by either increasing the repulsion energy barrier or inducing the steric interactions between QDs and the quartz sand collectors. A non-exponential decay characterized the retention profiles of QDs along the distance to the inlet. The modeling results indicated the four models containing the attachment, detachment, and straining terms - Model 1: M1-attachment, Model 2: M2-attachment and detachment, Model 3: M3-straining, and Model 4: M4-attachment, detachment, and straining - closely simulated the observed breakthrough curves (BTCs) but inadequately described the retention profiles.

The Effectiveness of Cyrene as a Solvent in Exfoliating 2D TMDs Nanosheets.

The pursuit of environmentally friendly solvents has become an essential research topic in sustainable chemistry and nanomaterial science. With the need to substitute toxic solvents in nanofabrication processes becoming more pressing, the search for alternative solvents has taken on a crucial role in this field. Additionally, the use of toxic, non-economical organic solvents, such as N-methyl-2 pyrrolidone and dimethylformamide, is not suitable for all biomedical applications, even though these solvents are often considered as the best exfoliating agents for nanomaterial fabrication. In this context, the success of producing two-dimensional transition metal dichalcogenides (2D TMDs), such as MoS2 and WS2, with excellent captivating properties is due to the ease of synthesis based on environment-friendly, benign methods with fewer toxic chemicals involved. Herein, we report for the first time on the use of cyrene as an exfoliating agent to fabricate monolayer and few-layered 2D TMDs with a versatile, less time-consuming liquid-phase exfoliation technique. This bio-derived, aprotic, green and eco-friendly solvent produced a stable, surfactant-free, concentrated 2D TMD dispersion with very interesting features, as characterized by UV-visible and Raman spectroscopies. The surface charge and morphology of the fabricated nanoflakes were analyzed using ς-potential and scanning electron microscopy. The study demonstrates that cyrene is a promising green solvent for the exfoliation of 2D TMD nanosheets with potential advantages over traditional organic solvents. The ability to produce smaller-sized-especially in the case of WS2 as compared to MoS2-and mono/few-layered nanostructures with higher negative surface charge values makes cyrene a promising candidate for various biomedical and electronic applications. Overall, the study contributes to the development of sustainable and environmentally friendly methods for the production of 2D nanomaterials for various applications.