Hexaethylene Glycol Research Articles

Fluorocarbon Vapors Slow Down Coalescence in Foams

AbstractControlling the stability of liquid foams is of the utmost importance for a wide range of applications. For decades, fluorocarbon vapors have been added to the gas phase of foams to ensure long‐term stability against bubble coarsening. However, it is shown here for the first time that they also have an unexpected and pronounced effect on bubble coalescence. This effect is quantified in detail for foams stabilized by the nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) at controlled fluorocarbon (perfluorohexane (C6F14)) concentrations, but it is observed for all investigated surfactants. Measuring surface tensions of the foaming solution with increasing fluorocarbon concentration, a synergy between the fluorocarbon and the surfactant is found which can be explained by a) the formation of mixed layers of both species at the gas/water interface at low fluorocarbon concentrations and b) the formation of a macroscopic fluorocarbon film if the gas phase is saturated with fluorocarbon vapor. The precise mechanism responsible for reducing coalescence, that is, film rupture, remains to be elucidated.

Emergence of Electric Fields at the Water-C12E6 Surfactant Interface.

We study the properties of the interface of water and the surfactant hexaethylene glycol monododecyl ether (C12E6) with a combination of heterodyne-detected vibrational sum frequency generation (HD-VSFG), Kelvin-probe measurements, and molecular dynamics (MD) simulations. We observe that the addition of the hydrogen-bonding surfactant C12E6, close to the critical micelle concentration (CMC), induces a drastic enhancement in the hydrogen bond strength of the water molecules close to the interface, as well as a flip in their net orientation. The mutual orientation of the water and C12E6 molecules leads to the emergence of a broad (∼3 nm) interface with a large electric field of ∼1 V/nm, as evidenced by the Kelvin-probe measurements and MD simulations. Our findings may open the door for the design of novel electric-field-tuned catalytic and light-harvesting systems anchored at the water-surfactant-air interface.

Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent.

Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C12TANO3/C12TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C12EO6) and octaethylene glycol monohexadecyl ether (C16EO8) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C12TANO3, C12TAB, C12EO6, and C16EO8 form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO3)3 in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.

The effect of C12E6 nonionic surfactant on the solubilization of Eosin Y in unmodified- and hydrophobically modified poly(Acrylic acid) solutions

The effect of the hexaethylene glycol mono-dodecyl ether (C12E6) on the solubilization of Eosin Yellow (2,4,5,7-tetrabromofluorescein, disodium salt) in 0.1 % wt. solution of unmodified and hydrophobically modified poly(acrylic acid) (PAA) was investigated by steady-state and dynamic fluorescence. To this end, firstly the poly(acrylic acid) was hydrophobically modified with 3 % mol and, respectively, 10 % mol linear C16 alkyl chain graft. The behavior of the obtained polymers and that of the parent one in the appropriate solvents were investigated by several methods. It was revealed that the grafts associated with the formation of intra-coil hydrophobic nano-domains and that the polyacrylic acids had lower viscosity than their sodium polyacrylates counterparts, although the c*s were almost similar. The effect of C12E6 nonionic surfactant on 0.1 % wt. polymers solution was also investigated. In water, the addition of C12E6 to polyacid solution leaded to the decrease of the critical aggregation concentration (CAC or T1). On the contrary, in the water–ethanol mixture the interaction was delayed, thus the CAC increased. At the addition of Eosin Y to the surfactant or surfactant-polymer solutions, the dye interacted with each species present in the system, no matter the solvent was. It was also shown that, at higher surfactant concentration, the dye solubilized into bound or free micelles. Therefore, it was considered the nonionic surfactant helped the anionic dye Eosin Y to be incorporated in poly(acrylic acid) based polymers.

Surface Activity of Ethoxylate Surfactants with Different Hydrophobic Architectures: The Effect of Layer Substructure on Surface Tension and Adsorption.

A series of nonionic ethoxylate surfactants containing different combinations of alkyl, phenyl, and adamantyl units in nine different arrangements, each combined with penta- and hexa-ethylene glycol groups, were synthesized and purified. The surface properties of all of the surfactants were investigated at the air-water (A-W) interface using surface tension (ST) to determine the limiting surface excess (Γlim), the limiting surface tension (σlim), and the critical micelle concentration (CMC). A smaller selection was investigated at the hydrophilic silica-water interface by neutron reflectometry to obtain the thickness of the adsorbed layer and the total adsorption at the CMC. An unusual and largely unrecognized feature of the ethoxylate group is that it is both hydrophilic and hydrophobic. It was found possible to account for the variation of σlim and Γlim of all of the adsorbed layers in terms of a balance of the estimated STs of the sublayers forming the overall adsorbed layer, including that of the underlying ethoxylate layer. The values of σlim were found to be highest for phenyl- and adamantyl-capped surfactants and lowest mainly when there was more than one methyl group at the surface. However, in terms of the concentration required to reach a given low ST, increasing the number of attached methyl groups was found to be less effective than using a smaller number of better-placed methyl groups. At the solid-liquid interface, adsorption at or above the CMC was in all cases in the form of a fragmented bilayer whose coverage varied approximately linearly with the packing parameter. However, results on the phenyl-capped surfactants showed that the high ST exhibited by these surfactants at the A-W interface becomes a high cohesion energy in the interior of the bilayer and they exhibited significantly higher adsorption than expected from simple packing arguments.

Sequence Preference and Initiator Promiscuity for De Novo DNA Synthesis by Terminal Deoxynucleotidyl Transferase.

The untemplated activity of terminal deoxynucleotidyl transferase (TdT) represents its most appealing feature. Its use is well established in applications aiming for extension of a DNA initiator strand, but a more recent focus points to its potential in enzymatic de novo synthesis of DNA. Whereas its low substrate specificity for nucleoside triphosphates has been studied extensively, here we interrogate how the activity of TdT is modulated by the nature of the initiating strands, in particular their length, chemistry, and nucleotide composition. Investigation of full permutational libraries of mono- to pentamers of d-DNA, l-DNA, and 2′O-methyl-RNA of differing directionality immobilized to glass surfaces, and generated via photolithographic in situ synthesis, shows that the efficiency of extension strongly depends on the nucleobase sequence. We also show TdT being catalytically active on a non-nucleosidic substrate, hexaethylene glycol. These results offer new perspectives on constraints and strategies for de novo synthesis of DNA using TdT regarding the requirements for initiation of enzymatic generation of DNA.

An Improved PEG-Linked Solid Support for Minimizing Process-Related Impurities During Solid-Phase Synthesis of DNA and RNA Sequences.

The preparation of controlled pore glass (CPG) supports, functionalized with several hexaethylene glycol spacers, to alleviate the problems associated with the porosity of commercial CPG supports is described in this article. The pore size of CPG restricts the diffusion of reagents to the leader nucleoside embedded in porous supports; this inhibits efficient solid-phase syntheses of DNA and RNA sequences and, by default, the purity of those sequences through formation of a shorter than full-length oligonucleotide. Functionalization of a CPG support with five hexaethylene glycol spacers led to a 42% reduction in process-related impurities contaminating oligonucleotide sequences, compared to that obtained using the commercial long-chain alkylamine (LCAA) CPG support. © 2021 Wiley Periodicals LLC. This article has been contributed to by US Government employees and their work is in the public domain in the USA. Basic Protocol 1: Preparation of the hydroxylated CPG support 3 Basic Protocol 2: Automated preparation of the CPG support 6 Basic Protocol 3: Automated preparation of the poly(hexaethylene glycol)-derived CPG 7 Basic Protocol 4: Automated functionalization of the poly(hexaethylene glycol)-derived CPG support 7 with leader deoxyribo- and ribonucleosides to provide the CPG support 9 Basic Protocol 5: Automated syntheses of DNA and RNA sequences on poly(hexaethylene glycol)-derived CPG support 9 and on a commercial long-chain alkylamine (LCAA) CPG support Support Protocol: Release and deprotection of the DNA and RNA sequences linked to the poly(hexaethylene glycol)-derived CPG support 10 and commercial LCAA-CPG support Basic Protocol 6: Comparative RP-HPLC analyses of crude, fully deprotected DNA or RNA sequences released from the poly(hexaethylene glycol)-derived CPG support 10 and from a commercial LCAA-CPG support.

Sigmoidal Dependence of Electrical Conductivity of Thin PEDOT:PSS Films on Concentration of Linear Glycols as a Processing Additive.

We investigate the sigmoidal concentration dependence of electrical conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) processed with linear glycol-based additives such as ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), hexaethylene glycol (HEG), and ethylene glycol monomethyl ether (EGME). We observe that a sharp transition of conductivity occurs at the additive concentration of ~0.6 wt.%. EG, DEG, and TEG are effective in conductivity enhancement, showing the saturation conductivities of 271.8, 325.4, and 326.2 S/cm, respectively. Optical transmittance and photoelectron spectroscopic features are rather invariant when the glycols are used as an additive. Two different figures of merit, calculated from both sheet resistance and optical transmittance to describe the performance of the transparent electrodes, indicate that both DEG and TEG are two most effective additives among the series in fabrication of transparent electrodes based on PEDOT:PSS films with a thickness of ~50–60 nm.

Surface Integrity of Dimethacrylate Composite Resins with Low Shrinkage Comonomers.

The goal of current research was to investigate the influence of adding low shrinkage “Phene” like comonomers hexaethylene glycol bis(carbamate-isoproply-α-methylstyrene) (HE-Phene) and triethylene glycol bis(carbamate-isoproply-α-methylstyrene) (TE-Phene) on the surface and color characteristics of composite resin. A range of weight fractions (0, 10, 20, 30, 40 wt.%) of HE/TE-Phene monomers were mixed with bisphenol A glycidyl methacrylate (GMA)/triethylene glycol dimethacrylate (TEGDMA) monomer. Experimental composite resins were made by mixing 71 wt.% of silica fillers to 29 wt.% of the resin matrix. A Vickers indenter and glossmeter were used for testing surface hardness (SH) and gloss (SG) at 60°. A chewing-simulator was used to evaluate the surface wear after 15,000 cycles. Color change (∆E) and translucency parameter (TP) were measured using a spectrophotometer. Data showed that HE/TE-Phene monomer had no negative impact (p > 0.05) on surface gloss, wear, color change and translucency of experimental composite resins. Surface hardness was in a reducing direction with the increas in HE/TE-Phene weight fraction (p < 0.05). The study results suggested that incorporating HE/TE-Phene monomers up to 30 wt.% with Bis-GMA/TEGDMA resin did not negatively influence the surface integrity of composite resins except for SH.

What happens when pesticides are solubilised in binary ionic/zwitterionic-nonionic mixed micelles?

HypothesisSurfactants have been widely used as adjuvants in agri-sprays to enhance the solubility of pesticides in foliar spray deposits and their mobility through leaf cuticles. Previously, we have characterised pesticide solubilisation in nonionic surfactant micelles, but what happens when pesticides become solubilised in anionic, cationic and zwitterionic and their mixtures with nonionic surfactants remain poorly characterised. ExperimentsTo facilitate characterisations by SANS and NMR, we used nonionic surfactant hexaethylene glycol monododecyl ether (C12E6), anionic sodium dodecylsulphate (SDS), cationic dodecyltrimethylammonium bromide (DTAB) and zwitterionic dodecylphosphocholine (C12PC) as model adjuvant systems to solubilise 3 pesticides, Cyprodinil (CP), Azoxystrobin (AZ) and Difenoconazole (DF), representing different structural features. The investigation focused on the influence of solubilisates in driving changes to the micellar nanostructures in the absence or presence of electrolytes. NMR and NOESY were applied to investigate the solubility and location of each pesticide in the micelles. SANS was used to reveal subtle changes to the micellar structures due to pesticide solubilisation with and without electrolytes. FindingsUnlike nonionic surfactants, the ionic and zwitterionic surfactant micellar structures remain unchanged upon pesticide solubilisation. Electrolytes slightly elongate the ionic surfactant micelles but have no effect on nonionic and zwitterionic surfactants. Pesticide solubilisation could alter the structures of the binary mixtures of ionic/zwitterionic and ionic/nonionic micelles by causing elongation, shell shrinkage and dehydration, with the exact alteration being determined by the molar ratio in the mixture.

An expedient process for reducing the formation of process-related impurities during solid-phase synthesis of potential nucleic acid-based drugs

With the intent of mitigating the formation of process-related impurities during solid-phase synthesis of DNA or RNA sequences, a hydroxylated controlled-pore glass support conjugated to three, five or seven hexaethylene glycol spacers was prepared and demonstrated to provide a more efficient and robust synthesis process. Indeed, the use of a support conjugated to five hexaethylene glycol spacers led to a 19% up to 42% reduction of process-related impurities contaminating synthetic nucleic acid sequences, when compared to that obtained from the same DNA/RNA sequences synthesized using a commercial long-chain alkylamine controlled-pore glass support under highly similar conditions.

Breakdown of the Stokes-Einstein Equation for Solutions of Water in Oil Reverse Micelles.

An experimental study is presented for the reverse micellar system of 15% by mass polydisperse hexaethylene glycol monodecylether (C10E6) in cyclohexane with varying amounts of added water up to 4% by mass. Measurements of viscosity and self-diffusion coefficients were taken as a function of temperature between 10 and 45 °C at varying sample water loads but fixed C10E6/cyclohexane composition. The results were used to inspect the validity of the Stokes-Einstein equation for this system. Unreasonably small reverse average micelle radii and aggregation numbers were obtained with the Stokes-Einstein equation, but reasonable values for these quantities were obtained using the ratio of surfactant-to-cyclohexane self-diffusion coefficients. While bulk viscosity increased with increasing water load, a concurrent expected decrease of self-diffusion coefficient was only observed for the surfactant and water but not for cyclohexane, which showed independence of water load. Moreover, a spread of self-diffusion coefficients was observed for the protons associated with the ethylene oxide repeat unit in samples with polydisperse C10E6 but not in a sample with monodisperse C10E6. These findings were interpreted by the presence of reverse micelle to reverse micelle hopping motions that with higher water load become increasingly selective toward C10E6 molecules with short ethylene oxide repeat units, while those with long ethylene oxide repeat units remain trapped within the reverse micelle because of the increased hydrogen bonding interactions with the water inside the growing core of the reverse micelle. Despite the observed breakdown of the Stokes-Einstein equation, the temperature dependence of the viscosities and self-diffusion coefficients was found to follow Arrhenius behavior over the investigated range of temperatures.

Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether

HypothesisPolyoxometalates (POMs) are metal oxygen clusters with a range of interesting magnetic and catalytic properties. POMs with attached hydrocarbon chains show amphiphilic behaviour so we hypothesised that mixtures of a nonionic surfactant and anionic surfactants with a polyoxometalate cluster as headgroup would form mixed micelles, giving control of the POM density in the micelle, and which would differ in size and shape from micelles formed by the individual surfactants. Due to the high charge and large size of the POM, we suggested that these would be nonideal mixtures due to the complex interactions between the two types of surfactants. The nonideality and the micellar composition may be quantified using regular solution theory. With supplementary information provided by small-angle neutron scattering (SANS), an understanding of this unusual binary surfactant system can be established. ExperimentsA systematic study was performed on mixed surfactant systems containing polyoxometalate-headed amphiphiles (K10[P2W17O61OSi2(CnH2n+1)2], abbreviated as P2W17-2Cn, where n = 12, 14 or 16) and hexaethylene glycol monododecyl ether (C12EO6). Critical micelle concentrations (CMCs) of these mixtures were measured and used to calculate the interaction parameters based on regular solution theory, enabling prediction of micellar composition. Predictions were compared to micelle structures obtained from SANS. A phase diagram was also established. FindingsThe CMCs of these mixtures suggest unusual unfavourable interactions between the two species, despite formation of mixed micelles. Micellar compositions obtained from SANS concurred with those calculated using the averaged interaction parameters for P2W17-2Cn/C12EO6 (n = 12 and 14). We attribute the unfavourable interactions to a combination of different phenomena: counterion-mediated interactions between P2W17 units and the unfolding of the ethylene oxide headgroups of the nonionic surfactant, yet micelles still form in these systems due to the hydrophobic interactions between surfactant tails.

Physicochemical properties of dimethacrylate resin composites with comonomer of Hexa/Tri-ethylene glycol bis(carbamate-isoproply-α-methylstyrene)

New photocurable “Phene” like monomers Hexaethylene glycol bis(carbamate-isoproply-α-methylstyrene) (HE-Phene) and Triethylene glycol bis(carbamate-isoproply-α-methylstyrene) (TE-Phene) were synthesized and incorporated into Bis-GMA/TEGDMA with the aim of reducing polymerization shrinkage without detriment to the physical and handling properties of the resin composites. Phene like monomers (HE/TE-Phene) were synthesized through a one-step reaction route, and their structures were confirmed by FT-IR and 1H-NMR spectra. HE/TE-Phene were incorporated into Bis-GMA/TEGDMA (50/50,wt/wt) with a series of mass fraction (from 0 wt.% to 40 wt.%). Experimental resin composites were prepared by mixing 29 wt.% of resin matrix to 71 wt.% of particulate-fillers. Degree of conversion (DC) was determined by FT-IR analysis. The volumetric shrinkage (VS) was calculated as a buoyancy change in distilled water by means of the Archimedes principle. Polymerization shrinkage-stress (SS) was measured using the tensilometer technique. The flexural strength (FS), modulus (FM), and fracture toughness (FT) were measured using a three-point bending setup. Viscosity was analyzed with a rotating disk rheometer. Water sorption and solubility were also measured. ANOVA analysis showed that DC (after 40 s), VS, and SS were in a trend of decreasing with the increasing of HE/TE-Phene concentration. In general, the experimental resin composites had comparable FT, FS and FM (p > 0.05) when the mass fraction of HE/TE-Phene in resin matrix was not more than 30 wt.%. The overall tested properties prove that including HE/TE-Phene up to 30 wt.% into Bis-GMA/TEGDMA resin could be potentially useful in the formulation of low-shrinkage resin composites.

Defining the Design Parameters for in Vivo Enzyme Delivery Through Protein Spherical Nucleic Acids.

The translation of proteins as effective intracellular drug candidates is limited by the challenge of cellular entry and their vulnerability to degradation. To advance their therapeutic potential, cell-impermeable proteins can be readily transformed into protein spherical nucleic acids (ProSNAs) by densely functionalizing their surfaces with DNA, yielding structures that are efficiently taken up by cells. Because small structural changes in the chemical makeup of a conjugated ligand can affect the bioactivity of the associated protein, structure–activity relationships of the linker bridging the DNA and the protein surface and the DNA sequence itself are investigated on the ProSNA system. In terms of attachment chemistry, DNA-based linkers promote a sevenfold increase in cellular uptake while maintaining enzymatic activity in vitro as opposed to hexaethylene glycol (HEG, Spacer18) linkers. Additionally, the employment of G-quadruplex-forming sequences increases cellular uptake in vitro up to fourfold. When translating to murine models, the ProSNA with a DNA-only shell exhibits increased blood circulation times and higher accumulation in major organs, including lung, kidney, and spleen, regardless of sequence. Importantly, ProSNAs with an all-oligonucleotide shell retain their enzymatic activity in tissue, whereas the native protein loses all function. Taken together, these results highlight the value of structural design in guiding ProSNA biological fate and activity and represent a significant step forward in the development of intracellular protein-based therapeutics.

A study on the uniqueness of advancing contact angle for a sessile drop of surfactant solutions

Abstract This study investigated the uniqueness of advancing contact angle (CA) by examining the evaporation process of a sessile drop of surfactant solution [sodium dodecyl sulfate (SDS), hexaethylene glycol monododecyl ether (C12E6) and Triton X-100 (TX-100)] on parafilm. The sessile drop was formed from a pendant drop that had reached its equilibrium surface tension in an atmosphere with ∼100% humidity. The relaxation of the drop profile and wetting diameter were recorded from the moment the drop touched the parafilm, and the data were then analyzed to determine the advancing CA. The results showed that for SDS solution drops, only one advancing CA was observed at each SDS concentration. However, the experimental data of TX-100 and C12E6 solution drops indicated the presence of two distinct regions that showed a near-constant CA with a quasi-equilibrium advance of the triple line; hence matching the definition of an advancing CA. The possibility of the existence of two advancing CA was further explored and the presence of two advancing CA for the sessile drops of TX-100 and C12E6 solution was verified by closely examining the advance of the triple line.

How does solubilisation of plant waxes into nonionic surfactant micelles affect pesticide release?

HypothesisNonionic surfactants are used as adjuvants in agri-sprays to stabilise pesticides, but what happens when pesticide-loaded micelles are brought into direct contact with plant leaves? As pesticide solubilisation dehydrates the micellar shell and increases the effective hydrophobicity of the surfactant, we hypothesise that these micelles would uptake plant waxes and alter the amount of pesticide solubilized as a result of the re-equilibrating process. ExperimentsThe solubility of the pesticide cyprodinil (CP) and its effect on the shape of hexaethylene glycol monododecyl ether (C12E6) micelles were studied using changes in cloud point, nuclear magnetic resonance (NMR), cryogenic transmission electron microscopy (Cryo-TEM) and small-angle neutron scattering (SANS). Similarly, the solubility of wheat leaf waxes was examined, as was the effect of adding leaf waxes to pre-dissolved cyprodinil in micellar C12E6. FindingsWax solubilisation caused pesticide release and shell hydration, and shortened the length of the cylindrical micelles of the CP loaded C12E6. Temperature increase led to a significant rise in the amount of the dissolved waxes, increased pesticide release, increased micellar length, and caused shrinkage and dehydration of the shell. This study indicates that agrochemical sprays are capable of dissolving leaf waxes, and may trigger pesticide release from surfactant micelles upon contact with plant surfaces.

Reversible Hydrogel Photopatterning: Spatial and Temporal Control over Gel Mechanical Properties Using Visible Light Photoredox Catalysis.

There is a growing interest in being able to control the mechanical properties of hydrogels for applications in materials, medicine, and biology. Primarily, changes in the hydrogel's physical properties, i.e., stiffness, toughness, etc., are achieved by modulating the network cross-linking chemistry. Common cross-linking strategies rely on (i) irreversible network bond degradation and reformation in response to an external stimulus, (ii) using dynamic covalent chemistry, or (iii) isomerization of integrated functional groups (e.g., azobenzene or spiropyran). Many of these strategies are executed using ultraviolet or visible light since the incident photons serve as an external stimulus that affords spatial and temporal control over the mechanical adaptation process. Here, we describe a different type of hydrogel cross-linking strategy that uses a redox-responsive cross-linker, incorporated in poly(hydroxyethyl acrylate)-based hydrogels at three different weight percent loadings, which consists of two viologen subunits tethered by hexaethylene glycol and capped with styrene groups at each terminus. These dicationic viologen subunits (V2+) can be reduced to their monoradical cations (V•+) through a photoinduced electron transfer (PET) process using a visible light-absorbing photocatalyst (tris(bipyridine)ruthenium(II) dichloride) embedded in the hydrogel, resulting in the intramolecular stacking of viologen radical cations, through radical-radical pairing interactions, while losing two positive charges and the corresponding counteranions from the hydrogel. It is shown how this concerted process ultimately leads to collapse of the hydrogel network and significantly (p < 0.05) increases (by nearly a factor of 2) the soft material's stiffness, tensile strength, and percent elongation at break, all of which is easily reversed via oxidation of the viologen subunits and swelling in water. Application of this reversible PET process was demonstrated by photopatterning the same hydrogel multiple times, where the pattern was "erased" each time by turning off the blue light (∼450 nm) source and allowing for oxidation and reswelling in between patterning steps. The areas of the hydrogel that were masked exhibited lower (by 1-2 kPa) shear storage moduli (G') than the areas that were irradiated for 1.5 h. Moreover, because the viologen subunits in the functional cross-linker are electrochromic, it is possible to visualize the regions of the hydrogel that undergo changes in mechanical properties. This visualization process was illustrated by photopatterning a larger hydrogel (∼9.5 cm on its longest side) with a photomask in the design of an array of stars.

Effects of Salt and Surfactant on Interfacial Characteristics of Water/Oil Systems: Molecular Dynamic Simulations and Dissipative Particle Dynamics

Multiphase systems and their behaviors/characteristics appear to be crucial in a variety of industries such as the oil and gas sector, pharmaceutical industry, and food industry. In this paper, the mesoscale simulation method is used to predict the interfacial behaviors of the water/oil systems at different temperatures and salt concentrations in the presence of a nonionic surfactant (hexaethylene glycol monododecyl ether). Dissipative particle dynamics (DPD) is employed to model the interfacial properties (e.g., interfacial density and interfacial tension) and structural properties such as the radius of gyration as a function of water/oil ratio, surfactant concentration, temperature, and salinity of oil/surfactant/water mixtures. Molecular dynamics (MD) simulations are carried out to estimate the Flory–Huggins chi parameter by means of temperature-dependent solubility parameter and cohesive energy calculations using Monte Carlo (MC) method, which is then utilized as an input for the DPD approach. The DPD...

What happens when pesticides are solubilized in nonionic surfactant micelles

Nonionic surfactants have been widely used in agri-sprays to enhance the solubility and mobility of pesticides, but what happens when pesticides become solubilized into surfactant micelles remains poorly characterized. To facilitate physical characterisations, we used the nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) as a model system to solubilize 4 pesticides including Cyprodinil (CP), Diuron (DN), Azoxystrobin (AZ) and Difenoconazole (DF). The investigation focused on the influence of solubilizate and temperature in driving changes to the micellar nanostructures. Dynamic light scattering (DLS), cryogenic transmission electron microscopy (Cryo-TEM) and small-angle neutron scattering (SANS) measurements were used to reveal changes to the micellar structure before and after pesticide solubilisation. Nuclear magnetic resonance (NMR) was also applied to investigate the solubility and location of each pesticide in the micelles. Pesticides clearly altered the micellar structure, by increasing the aggregation number and micellar lengths, whilst shrinking and dehydrating the shells, leading to a consequent decrease in the dispersion cloud points. Increases in temperature affected micellar structures in a similar way. Thus, temperature increases and the solubilisation of pesticides can both make the surfactant effectively more hydrophobic, altering the micellar nanostructures and shifting the pesticide location within the micelles. These changes subsequently implicate how pesticides are delivered into plants through the natural wax films.