Understanding interactions of plasticisers with a phospholipid monolayer.

The use of DEHP (diethylhexyl phthalate) is now banned for most applications in Europe; the exception is for blood bags, where its toxicity is overshadowed by its ability to extend the storage life of red blood cells. Another plasticiser, BTHC (butanoyl trihexyl citrate), is used in paediatric blood bags but does not stabilise blood cells as effectively. Interactions between plasticisers and lipids are investigated with a phospholipid, DMPC, to understand the increased stability of blood cells in the presence of DEHP as well as bioaccumulation and identify differences with BTHC. Mixed monolayers of DMPC and DEHP or BTHC were studied on Langmuir troughs where surface pressure/area isotherms can be measured. Neutron reflection measurements were made to determine the composition and structure of these mixed layers. A large amount of plasticiser can be incorporated into a DMPC monolayer but once an upper limit is reached, plasticiser is selectively removed from the interface at high surface pressures. The upper limit is found to occur between 40-60 mol% for DEHP and 20-40 mol% for BTHC. The areas per molecule are also different with DEHP being in the range of 50-100 Å2 and BTHC being 65-120 Å2. Results indicate that BTHC does not fit as well as DEHP in DMPC monolayers which could help explain the differences observed with regards to the stability of blood cells.

N-Rich Bilayer Solid Electrolyte Interphase toward Highly Reversible Lithium Metal Batteries.

Continuous lithium (Li)/electrolyte interfacial reactions and uncontrollable Li dendrites severely hamper the application of paradigmatic Li metal batteries (LMBs). Aiming to address the above-mentioned crucial issues, N-rich polymer-inorganic bilayers at the Li/electrolyte interface are designed via nitrate-rich electrolytes, achieving high-energy-density and long-lifespan LMBs. The inner layer of Li3N favors rapid and uniform Li+ deposition, while the outer layer of N-containing flexible polymers facilitates uniform Li+ distribution at the interlayer and accommodates volume changes during cycling. The synergistic effect of N-rich polymer-inorganic bilayers promotes the formation of dense uniform spherical nuclei morphology instead of dendrites, thus significantly improving the plating-stripping reversibility of LMBs. Attributed to the unique interphase, the Li|Li cell can stably run for over 1000 h at 1.0 mA cm-2 with an even deposition morphology, which is monitored and proven by in situ optical microscopy. Moreover, the assembled Li|S cell displays a high capacity of 697.6 mA h g-1 for over 150 cycles and a 99% Coulombic efficiency. This work paves the way for designing high-energy and long-lifespan LMBs.

Self-Assembling Anti-Freezing Lamellar Nanostructures in Subzero Temperatures.

The requirement for cryogenic supramolecular self-assembly of amphiphiles in subzero environments is a challenging topic. Here, the self-assembly of lamellar lyotropic liquid crystals (LLCs) are presented to a subzero temperature of -70 °C. These lamellar nanostructures are assembled from specifically tailored ultra-long-chain surfactant stearyl diethanolamine (SDA) in water/glycerol binary solvent. As the temperature falls below zero, LLCs with a liquid-crystalline Lα phase, a tilted Lß phase, and a new folded configuration are obtained consecutively. A comprehensive experimental and computational study is performed to uncover the precise microstructure and formation mechanism. Both the ultra-long alkyl chain and head group of SDA play a crucial role in the formation of lamellar nanostructures. SDA head group is prone to forming hydrogen bonds with water, rather than glycerol. Glycerol cannot penetrate the lipid layer, which mixes with water arranging outside of the lipid bilayer, providing an ideal anti-freezing environment for SDA self-assembly. Based on these nanostructures and the ultra-low freezing point of the system, a series of novel cryogenic materials are created with potential applications in extremely cold environments. These findings would contribute to enriching the theory and research methodology of supramolecular self-assembly in extreme conditions and to developing novel anti-freezing materials.

Structure and interaction of therapeutic proteins in solution: a combined simulation and experimental study.

The aggregation of therapeutic proteins in solution has attracted significant interest, driving efforts to understand the relationship between microscopic structural changes and protein-protein interactions determining aggregation processes in solution. Additionally, there is substantial interest in being able to predict aggregation based on protein structure as part of molecular developability assessments. Molecular Dynamics provides theoretical tools to complement experimental studies and to interrogate and identify the microscopic mechanisms determining aggregation. Here we perform all-atom MD simulations to study the structure and inter-protein interaction of the Fab and Fc fragments of the monoclonal antibody (mAb) COE3. We unravel the role of ion-protein interactions in building the ionic double layer and determining effective inter-protein interaction. Further, we demonstrate, using various state-of-the-art force fields (charmm, gromos, amber, opls/aa), that the protein solvation, ionic structure and protein-protein interaction depend significantly on the force field parameters. We perform SANS and Static Light Scattering experiments to assess the accuracy of the different forcefields. Comparison of the simulated and experimental results reveal significant differences in the forcefields' performance, particularly in their ability to predict the protein size in solution and inter-protein interactions quantified through the second virial coefficients. In addition, the performance of the forcefields is correlated with the protein hydration structure.

Evidence for an L3 phase in ternary deep eutectics: composition-induced L3-to-Lα transition of AOT.

Pure and hydrated deep eutectic solvents (DES) are proposed to form self-assembled nanostructures within the fluid bulk, similar to the bicontinuous L3 phase common for ionic liquids (ILs). Labelled choline chloride : urea : water DES were measured using small-angle neutron scattering (SANS), showing no long-range nanostructure. However, solutions of the surfactant AOT in this DES yielded scattering consistent with the L3 "sponge" phase, which was fitted using the Teubner-Strey model. A disclike model gave local structural information, namely, a linear increase in radius versus solvent water content (w = molar ratio of DES : water), eventually forming large, turbid lamellar phases at 10w; an L3-to-Lα transition was observed. Simultaneous multi-contrast SANS fits show the surfactant headgroup region is dominated by interactions with poorly-soluble Na+ at low water contents, and numerically-superior [cholinium]+ as water content increases. The modified interfacial Gaussian curvature from cation : anion volume matching stabilizes the lamellar morphology, allowing the bilayer aggregation number to increase.

Pathogenicity and epidemiological survey of fowl adenovirus in Shandong Province from 2021 to 2022.

In recent years, the poultry industry had been markedly affected by adenoviral diseases such as hydropericardium syndrome and inclusion body hepatitis caused by fowl adenovirus (FAdV), which have become increasingly prevalent in China. Shandong Province, China, is an important area for poultry breeding where various complex and diverse FAdV serotypes were isolated. However, the dominant strains and their pathogenic characteristics are not yet reported. Therefore, a pathogenicity and epidemiological survey of FAdV was conducted, showing that the local dominant serotypes of FAdV epidemics were FAdV-2, FAdV-4, FAdV-8b, and FAdV-11. Their mortality rates in the 17-day-old specific-pathogen-free (SPF) chicks ranged from 10 to 80%; clinical signs included mental depression, diarrhea, and wasting. The maximum duration of viral shedding was 14 days. The highest incidence in all infected groups was on days 5-9, and then gradual regression occurred thereafter. The most pronounced symptoms occurred in chicks infected with FAdV-4, including pericardial effusion and inclusion body hepatitis lesions. Our results add to the current epidemiological data on FAdV in poultry flocks in Shandong and elucidate the pathogenicity of dominant serotypes. This information may be important for FAdV vaccine development and comprehensive epidemic prevention and control.

Competitive Adsorption of a Monoclonal Antibody and Nonionic Surfactant at the PDMS/Water Interface.

Interfacial adsorption of monoclonal antibodies (mAbs) can cause structural deformation and induce undesired aggregation and precipitation. Nonionic surfactants are often added to reduce interfacial adsorption of mAbs which may occur during manufacturing, storage, and/or administration. As mAbs are commonly manufactured into ready-to-use syringes coated with silicone oil to improve lubrication, it is important to understand how an mAb, nonionic surfactant, and silicone oil interact at the oil/water interface. In this work, we have coated a polydimethylsiloxane (PDMS) nanofilm onto an optically flat silicon substrate to facilitate the measurements of adsorption of a model mAb, COE-3, and a commercial nonionic surfactant, polysorbate 80 (PS-80), at the siliconized PDMS/water interface using spectroscopic ellipsometry and neutron reflection. Compared to the uncoated SiO2 surface (mimicking glass), COE-3 adsorption to the PDMS surface was substantially reduced, and the adsorbed layer was characterized by the dense but thin inner layer of 16 Å and an outer diffuse layer of 20 Å, indicating structural deformation. When PS-80 was exposed to the pre-adsorbed COE-3 surface, it removed 60 wt % of COE-3 and formed a co-adsorbed layer with a similar total thickness of 36 Å. When PS-80 was injected first or as a mixture with COE-3, it completely prevented COE-3 adsorption. These findings reveal the hydrophobic nature of the PDMS surface and confirm the inhibitory role of the nonionic surfactant in preventing COE-3 adsorption at the PDMS/water interface.

Retrospective Investigation and Genetic Variation Analysis of Chicken Infectious Anemia in Shandong Province, 2020-2022.

Chicken infectious anemia (CIA) is a vertical transmission infectious chicken disease caused by the chicken infectious anemia virus (CAV). The disease can induce stunting and immunosuppression in chicks by infecting bone marrow-derived stem cells, causing huge economic losses for the poultry industry. To determine the prevalence of CIA in Shandong Province, China, 854 suspected CIA samples were collected and analyzed in 13 cities in Shandong from 2020 to 2022. The PCR results showed that a total of 115 CAV were isolated. The CAV-positive rates were 17.21% (26/151) in 2020, 12.23% (35/286) in 2021, and 12.94% (54/417) in 2022, with severe mixed infections. Among them, CAV and fowl adenovirus (FAdV) were the most common, accounting for 40.86%. VP1 gene homology analysis showed that isolated strains shared 96.1-100% homology with the previously reported CAV strains. Genetic variation analysis showed that most of the isolated CAV strains were located in genotype A. These results indicate that CIA infection in Shandong chickens in recent years has been prevalent and mixed infections are common, but there were no significant genetic variations. Our results extend the understanding of the prevalence and genetic evolution of CIA in Shandong Province. They will offer new references for further study of the epidemiology and virus variation and the prevention and control of this disease.

Acidification-Induced Structure Evolution of Lipid Nanoparticles Correlates with Their In Vitro Gene Transfections.

The rational design of lipid nanoparticles (LNPs) for enhanced gene delivery remains challenging because of incomplete knowledge of their formulation-structure relationship that impacts their intracellular behavior and consequent function. Small-angle neutron scattering has been used in this work to investigate the structure of LNPs encapsulating plasmid DNA upon their acidification (from pH 7.4 to 4.0), as would be encountered during endocytosis. The results revealed the acidification-induced structure evolution (AISE) of the LNPs on different dimension scales, involving protonation of the ionizable lipid, volume expansion and redistribution of aqueous and lipid components. A similarity analysis using an LNP's structural feature space showed a strong positive correlation between function (measured by intracellular luciferase expression) and the extent of AISE, which was further enhanced by the fraction of unsaturated helper lipid. Our findings reveal molecular and nanoscale changes occurring during AISE that underpin the LNPs' formulation-nanostructure-function relationship, aiding the rational design of application-directed gene delivery vehicles.

Surfactant induced gelation of TEMPO-oxidized cellulose nanofibril dispersions probed using small angle neutron scattering.

In this work, we studied TEMPO-oxidized cellulose nanofibril (OCNF) suspensions in the presence of diverse surfactants. Using a combination of small angle neutron scattering (SANS) and rheology, we compared the physical properties of the suspensions with their structural behavior. Four surfactants were studied, all with the same hydrophobic tail length but different headgroups: hexaethylene glycol mono-n-dodecyl ether (C12EO6, nonionic), sodium dodecyl sulfate (SDS, anionic), cocamidopropyl betaine (CapB, zwitterionic), and dodecyltrimethylammonium bromide (DTAB, cationic). Contrast variation SANS studies using deuterated version of C12EO6 or SDS, or by varying the D2O/H2O ratio of the suspensions (with CapB), allowed focusing only on the structural properties of OCNFs or surfactant micelles. We showed that, in the concentration range studied, for C12EO6, although the nanofibrils are concentrated thanks to an excluded volume effect observed in SANS, the rheological properties of the suspensions are not affected. Addition of SDS or CapB induces gelation for surfactant concentrations superior to the critical micellar concentration (CMC). SANS results show that attractive interactions between OCNFs arise in the presence of these anionic or zwitterionic surfactants, hinting at depletion attraction as the main mechanism of gelation. Finally, addition of small amounts of DTAB (below the CMC) allows formation of a tough gel by adsorbing onto the OCNF surface.

Effect of surfactants on the thermoresponse of PNIPAM investigated in the brush geometry.

HYPOTHESIS: Anionic surfactants have been reported to interact with poly(N-isopropyl acrylamide) (PNIPAM), suppressing its thermoresponse. Scattering and NMR studies of the anionic sodium dodecylsulfate (SDS) system propose that the PNIPAM-surfactant interaction is purely hydrophobic. However, prior phenomenological investigations of a range of surfactant identities (anionic, cationic, nonionic) show that only anionic surfactants affect the thermoresponse and conformation of PNIPAM, implying that the hydrophilic head-group also contributes. Crucially, the phenomenological experiments do not measure the affinity of the tested surfactants to the polymer, only their effect on its behaviour. EXPERIMENTS: We study the adsorption of six surfactants within a planar PNIPAM brush system, elucidating the polymer conformation, thermoresponse, and surfactant adsorption kinetics using ellipsometry, neutron reflectometry (NR), optical reflectometry and the quartz crystal microbalance technique. NR is used to measure the distribution of surfactants within the brush. FINDINGS: We find that only anionic surfactants modify the structure and thermoresponse of PNIPAM, with the greater affinity of anionic surfactants for PNIPAM (relative to cationic and nonionic surfactants) being the primary reason for this behaviour. These results show that the surfactant head-group has a more critical role in mediating PNIPAM-surfactant interaction than previously reported. Taking inspiration from prior molecular dynamics work on the PEO-surfactant system, we propose an interaction mechanism for PNIPAM and SDS that reconciles evidence for hydrophobic interaction with the observed head-group-dependent affinity.

Epidemiological survey of PRRS and genetic variation analysis of the ORF5 gene in Shandong Province, 2020-2021.

Since the rise of porcine reproductive and respiratory syndrome virus (PRRSV) in China, mutations have occurred regularly. In particular, the emergence of HP-PRRSV has significantly improved the pathogenicity of PRRSV. It has brought huge economic losses to the Chinese pig farming industry. To understand the current prevalence and evolution of PRRSV in Shandong Province, 1,344 samples suspected of having PRRSV were collected from local hog farms of different sizes. Genetic variation in the isolated PRRSV ORF5 gene was analyzed using the RT-PCR method. The results showed that the detection rate of PRRSV in the collected samples was 25.44%. The predominant strain of PRRSV in Shandong Province is still NADC30-like. However, it cannot be ignored that NADC34-like is also starting to become a prevalent strain. Mutations in ORF5 amino acids 13, 151 and neutralizing epitope (aa36-aa52) in some isolates can cause changes in virulence and ability to escape immunity. This study enriches the epidemiological data on PRRSV in Shandong Province, China. It provides an important reference for the development of new vaccines and for the prevention and control of PRRSV.

Structural investigation of sulfobetaines and phospholipid monolayers at the air-water interface.

Mixtures of sulfobetaine based lipids with phosphocholine phospholipids are of interest in order to study the interactions between zwitterionic surfactants and the phospholipids present in cell membranes. In this study we have investigated the structure of mixed monolayers of sulfobetaines and phosphocholine phospholipids. The sulfobetaine used has a single 18-carbon tail, and is referred to as SB3-18, and the phospholipid used is DMPC. Surface pressure-area isotherms of the samples were used to determine whether any phase transitions were present during the compression of the monolayers. Neutron and X-ray reflectometry were then used to investigate the structure of these monolayers perpendicular to the interface. We found that the average headgroup and tail layer thickness was reasonably consistent across all mixtures, with a variation of less than 3 Å reported in the total thickness of the monolayers at each surface pressure. However, by selective deuteration of the two components of the monolayers, it was found that the two components have different tail layer thicknesses. For the mixture with equal compositions of DMPC and SB3-18 or with a higher composition of DMPC the tail tilts were found to be constant, resulting in a greater tail layer thickness for SB3-18 due to its longer tail. For the mixture higher in SB3-18 this was not the case, the tail tilt angle for the two components was found to be different and DMPC was found to have a greater tail layer thickness than SB3-18 as a result.

Understanding the Stabilizing Effect of Histidine on mAb Aggregation: A Molecular Dynamics Study.

Histidine, a widely used buffer in monoclonal antibody (mAb) formulations, is known to reduce antibody aggregation. While experimental studies suggest a nonelectrostatic, nonstructural (relating to secondary structure preservation) origin of the phenomenon, the underlying microscopic mechanism behind the histidine action is still unknown. Understanding this mechanism will help evaluate and predict the stabilizing effect of this buffer under different experimental conditions and for different mAbs. We have used all-atom molecular dynamics simulations and contact-based free energy calculations to investigate molecular-level interactions between the histidine buffer and mAbs, which lead to the observed stability of therapeutic formulations in the presence of histidine. We reformulate the Spatial Aggregation Propensity index by including the buffer-protein interactions. The buffer adsorption on the protein surface leads to lower exposure of the hydrophobic regions to water. Our analysis indicates that the mechanism behind the stabilizing action of histidine is connected to the shielding of the solvent-exposed hydrophobic regions on the protein surface by the buffer molecules.

Small-angle neutron scattering from mixtures of long- and short-chain 3-alkyl-1-methyl imidazolium bistriflimides.

The preparation of mixtures of ionic liquids (ILs) represents an attractive strategy to tune their properties, an important aspect of which is to understand how the structure of the bulk varies with composition. In this study, small-angle neutron scattering (SANS) was used to probe mixtures of methylimidazolium-based ionic liquids [Cnmim][Tf2N] with [C2mim][Tf2N]) (n = 4, 6, 8 and 10) and of [Cmmim][Tf2N] with [C12mim][Tf2N] (m = 2, 4, 6 and 8). Mixtures were prepared in both contrasts, which is to say that one component would be fully hydrogenated while the other was fully deuterated, and vice versa. Data were fitted using a range of appropriate models, of which the Teubner-Strey model provided most useful information and the pure materials showed a nascent Polar Non-polar Peak (PNPP) for n = 6, which became more evident as n increased. In the mixtures [Cnmim]x[C2mim]1-x[Tf2N], the PNPP was evident for n = 10 and 8, nascent for n = 6 and absent for n = 4, with percolation showing a very strong dependence on the chain length of the added IL, [Cnmim][Tf2N]. In contrast, while the ability of [C12mim][Tf2N] to form percolated structures was damped when mixed with [Cmmim][Tf2N], as m increased from 2 to 6, this effect was less strong. However, data obtained for mixtures of [C12mim][Tf2N] and [C8mim][Tf2N], both of which percolate as pure materials, did not fit easily in any of the models applied to the previous systems and gave results that depended on the contrast used. Complementary small-angle X-ray scattering (SAXS) data, however, showed the expected evolution and behaviour of the PNPP, COP and CP, revealing that the unexpected observations were due to an adventitious matching out of isotopic contrasts. As well as revealing details of the structures of these IL mixtures, the results also point to complementary strategies for generating bulk percolated structures as a function of cation chain length.

Structural features of interfacially adsorbed acyl-l-carnitines.

HYPOTHESIS: Acyl-l-carnitines (CnLCs) are potentially important as biosurfactants in drug delivery and tissue engineering due to their good biocompatibility. However, little is currently known about the basic interfacial behavior underlying their technological applications. Following our previous characterization of their solution aggregation and adsorption at the air/water interface, this work examines how they adsorb at the hydrophilic solid/liquid interface. EXPERIMENTS: As the SiO2/water interface has served as the model substrate for many interfacial adsorption studies, so it has been used in this work as the solid substrate to facilitate dynamic adsorption by spectroscopic ellipsometry (SE) and structural determination of the adsorbed layers by neutron reflection (NR) under different conditions at the SiO2/water interface from a group of CnLC (n = 12, 14, and 16). FINDINGS: CnLC surfactants are zwitterionic at neutral pH. They reached saturated adsorption above their critical micellar concentrations (CMCs) and formed a sandwich bilayer with a head-tail-head structure at the hydrophilic SiO2/water interface. The total thicknesses of the adsorbed layers at CMC were found to be 33 ± 2, 35 ± 2, and 37 ± 2 Å for C12LC, C14LC, and C16LC, respectively, with their inner and outer head layers remaining similar but the thickness of the interdigitated middle layer increasing with acyl chain length. As the solution becomes acidic, the carboxyl groups become protonated and the l-carnitine heads are net positively charged, resulting in increased repulsion between the head groups. In this situation, the CnLC surfactants are adsorbed as distinct aggregates to reduce repulsive interaction, resulting in reduced surfactant volume fraction and layer thickness. However, a high ionic strength can screen the repulsive interaction and enhance the adsorbed amount, effectively diminishing the impact of pH. This information provides a useful basis for exploring the technological applications of CnLCs involving a solid substrate.

In-Membrane Nanostructuring of Cationic Amphiphiles Affects Their Antimicrobial Efficacy and Cytotoxicity: A Comparison Study between a De Novo Antimicrobial Lipopeptide and Traditional Biocides.

Cationic biocides have been widely used as active ingredients in personal care and healthcare products for infection control and wound treatment for a long time, but there are concerns over their cytotoxicity and antimicrobial resistance. Designed lipopeptides are potential candidates for alleviating these issues because of their mildness to mammalian host cells and their high efficacy against pathogenic microbial membranes. In this study, antimicrobial and cytotoxic properties of a de novo designed lipopeptide, CH3(CH2)12CO-Lys-Lys-Gly-Gly-Ile-Ile-NH2 (C14KKGGII), were assessed against that of two traditional cationic biocides CnTAB (n = 12 and 14), with different critical aggregation concentrations (CACs). C14KKGGII was shown to be more potent against both bacteria and fungi but milder to fibroblast host cells than the two biocides. Biophysical measurements mimicking the main features of microbial and host cell membranes were obtained for both lipid monolayer models using neutron reflection and small unilamellar vesicles (SUVs) using fluorescein leakage and zeta potential changes. The results revealed selective binding to anionic lipid membranes from the lipopeptide and in-membrane nanostructuring that is distinctly different from the co-assembly of the conventional CnTAB. Furthermore, CnTAB binding to the model membranes showed low selectivity, and its high cytotoxicity could be attributed to both membrane lysis and chemical toxicity. This work demonstrates the advantages of the lipopeptides and their potential for further development toward clinical application.

An insight into the thermo-thickening behavior of wormlike micellar solutions based on ultra-long-chain surfactants.

Generally, the solution viscosity of wormlike micelles (WLMs) assembled from common surfactants decreases upon an increase in the temperature, following the Arrhenius law. However, abnormal thermo-thickening behavior has been repeatedly observed for WLMs formed by ultra-long-chain (≥C18) surfactants. It would be useful to unravel the mechanism behind this phenomenon. Here, three C22-tailed surfactants with an erucyl tail, two of them containing carboxylate or sulfonate head groups (UC22DAB and UC22DAS) and a cationic one with an iodide counterion (UC22DAI), and two C18-tailed betaines with olemido- and stearamidopropyl hydrophobic chains (UC18DAS and C18DAS) were characterised in terms of their viscosity and viscoelastic behavior with increasing temperature to examine the roles of head groups, tail length and tail nature. Their micellar structures were elucidated at various temperatures using small angle neutron scattering (SANS), small angle neutron X-ray scattering (SAXS) and molecular dynamics simulation. It is found that the thermo-thickening behavior of ultra-long-chain surfactants is ascribed to the prolonged persistence length and increased entanglement points. When the temperature is increased, an increase in viscosity is always accompanied by a longer persistent length, thus a larger hydrodynamic volume. The iceberg structure around the hydrophobic tail of surfactants can be destroyed at high temperatures leading to the self-assembly of these surfactants. In this self-assembly process, compared to cationic surfactants, zwitterionic surfactants can form WLMs more readily due to weak electrostatic repulsions between their head groups; the longer tails give the surfactants enhanced hydrophobicity to form WLMs with a long breaking time; the cis-unsaturation and the resulting kink in the hydrophobic tails give the surfactants good solubility, which is not conducive to the formation of micelles. In brief, the zwitterionic, longer tail and saturated tail surfactants can form WLMs with a prolonged persistence length at elevated temperatures.

Contrasting impacts of mixed nonionic surfactant micelles on plant growth in the delivery of fungicide and herbicide.

HYPOTHESIS: Nonionic alkyl ethoxylate surfactants are widely used in agrochemicals to facilitate the permeation of systemic herbicides and fungicides across the plant waxy film. Industrial grade surfactants are often highly mixed and how the mixing affects their interactions with pesticides and wax films remains largely unexplored. A better understanding could enable design of mixed nonionic surfactants for herbicides and fungicides to maximize their efficiency and reduce wastage whilst controlling their impact on plant wax films. EXPERIMENT: In this study, nonionic surfactants with general structure n-oxyethylene glycol monododecyl ether (C12En) were used to form surfactant mixtures with the same average ethoxylate numbers but different hydrophilic-lipophilic balance (HLB) values. Their mixed micellar systems were then used to solubilize a herbicide diuron (DN) and a fungicide cyprodinil (CP), followed by plant wax solubilization upon contact with wax films. These processes were monitored by 1H NMR and SANS. FINDING: Pesticide solubilization made surfactant micelles effectively more hydrophobic but subsequent wax dissolution caused pesticide release and the restoration of the micellar amphiphilicity. Nonionic surfactants with lower HLBs form larger nanoaggregates, show enhanced wettability, and have better ability to solubilize and permeate pesticides across the wax film, but may cause significant damage to plant growth. These observations help explain why herbicides applied on weeds would benefit from surfactants with lower HLB values while fungicides require surfactants with HLBs to balance between delivery efficiency and potential phytotoxicity risks.

Strong synergistic interactions in zwitterionic-anionic surfactant mixtures at the air-water interface and in micelles: The role of steric and electrostatic interactions.

HYPOTHESIS: The milder interaction with biosystems makes the zwitterionic surfactants an important class of surfactants, and they are widely used in biological applications and in personal care formulations. An important aspect of those applications is their strong synergistic interaction with anionic surfactants. It is anticipated that the strong interaction will significantly affect the adsorption and self-assembly properties. EXPERIMENTS: Surface tension, ST, neutron reflectivity, NR, and small angle neutron scattering, SANS, have been used here to explore the synergistic mixing in micelles and at the air-water interface for the zwitterionic surfactant, dodecyldimethylammonium propanesulfonate, C12SB, and the anionic surfactants, alkyl ester sulfonate, AES, in the absence and presence of electrolyte, 0.1 M NaCl. FINDINGS: At the air-water interface the asymmetry of composition in the strong synergistic interaction and the changes with added electrolyte and anionic surfactant structure reflect the relative contributions of the electrostatic and steric interactions to the excess free energy of mixing. In the mixed micelles the synergy is less pronounced and indicates less severe packing constraints. The micelle structure is predominantly globular to elongated, and shows a pronounced micellar growth with composition which depends strongly upon the nature of the anionic surfactant and the addition of electrolyte.