In situ monitoring of latex film formation by small-angle neutron scattering: Evolving distributions of hydrophilic stabilizers in drying colloidal films

The distribution of hydrophilic species, such as surfactants, in latex films is of critical importance for the performance of adhesives, coatings and inks, among others. However, the evolution of this distribution during the film formation process and in the resulting dried films remains insufficiently elucidated. Here, we present in situ (wet) and ex situ (dry) SANS experiments that follow the film formation of two types of latex particles, which differ in their stabilizer: either a covalently bonded poly(methacrylic acid) (PMAA) segment or a physically adsorbed surfactant (sodium dodecyl sulfate, SDS). By fitting the experimental SANS data and combining with gravimetry experiments, we have ascertained the hydrophilic species distribution within the drying film and followed its evolution by correlating the size and shape of stabilizer clusters with the drying time. The evolution of the SDS distribution over drying time is being driven by a reduction in the interfacial free energy. However, the PMAA-based stabilizer macromolecules are restricted by their covalent bonding to core polymer chains and hence form high surface-area disc-like phases at the common boundary between particles and PMAA micelles. Contrary to an idealized view of film formation, the PMAA does not remain in the walls of a continuous honeycomb structure. The results presented here shed new light on the nanoscale distribution of hydrophilic species in drying and ageing latex films. We provide valuable insights into the influence of the stabilizer mobility on the final structure of latex films

Supporting Data for "Synthesis and electrokinetics of cationic spherical nanoparticles in salt-free non-polar media" (Chemical Science, doi:10.1039/c7sc03334f)

<p>TEM micrographs of diblock copolymer micelles (magnification given in file name).</p> <p>Small-angle X-ray (SAXS) and small-angle neutron scattering (SANS) data (Q [1/Å], I(Q) [SAXS - arbitrary, SANS - 1/cm], error I(Q) [same units]).</p

Aggregation Properties of <i>p</i>‑Phenylene Vinylene Based Conjugated Oligoelectrolytes with Surfactants

The amphiphilic properties of conjugated oligoelectrolytes (COE) and their sensitivity to the polarity of their microenvironment lead to interesting aggregation behavior, in particular in their interaction with surfactants. Photoluminescence (PL) spectroscopy, liquid-phase atomic force microscopy, small-angle neutron scattering, small-angle X-ray scattering, and grazing-incidence X-ray diffraction were used to examine interactions between cationic <i>p</i>-phenylene vinylene based oligoelectrolytes and surfactants. These techniques indicate the formation of COE/surfactant aggregates in aqueous solution, and changes in the photophysical properties are observed when compared to pure aqueous solutions. We evaluate the effect of the charge of the surfactant polar headgroup, the size of the hydrophobic chain, and the role of counterions. At low COE concentrations (micromolar), it was found that these COEs display larger emission quantum efficiencies upon incorporation into micelles, along with marked blue-shifts of the PL spectra. This effect is most pronounced in the series of anionic surfactants, and the degree of blue shifts as a function of surfactant charge is as follows: cationic < nonionic < anionic surfactants. In anionic surfactants, such as sodium dodecyl sulfate (SDS), the PL spectra show vibronic resolution above the critical micelle concentration of the surfactant, suggesting more rigid structures. Scattering data indicate that in aqueous solutions, trimers appear as essentially 3-dimensional particles, while tetra- and pentamers form larger, cylindrical particles. When the molar ratio of nonionic C₁₂E₅ surfactant to 1,4-bis­(4-{<i>N</i>,<i>N</i>-bis-[(<i>N</i>,<i>N</i>,<i>N</i>-trimethylammonium)­hexyl]­amino}-styryl)­benzene tetraiodide (DSBNI) is close to one, the size of the formed DSBNI-C₁₂E₅ particles corresponds to the full coverage of individual oligomers. When these particles are transferred into thin films, they organize into a cubic in-plane pattern. If anionic SDS is added, the formed DSBNI-SDS particles are larger than expected for full surfactant coverage, and particles may thus contain several oligomers. This tendency is attributed to the merging of DSBNI oligomers due to the charge screening and, thus, reduced water solubility

Tuning Micellar Structures in Supercritical CO₂ Using Surfactant and Amphiphile Mixtures

For equivalent micellar volume fraction (ϕ), systems containing anisotropic micelles are generally more viscous than those comprising spherical micelles. Many surfactants used in water-in-CO₂ (w/c) microemulsions are fluorinated analogues of sodium bis­(2-ethylhexyl) sulfosuccinate (AOT): here it is proposed that mixtures of CO₂-philic surfactants with hydrotropes and cosurfactants may generate elongated micelles in w/c systems at high-pressures (e.g., 100–400 bar). A range of novel w/c microemulsions, stabilized by new custom-synthesized CO₂-phillic, partially fluorinated surfactants, were formulated with hydrotropes and cosurfactant. The effects of water content (<i>w</i> = [water]/[surfactant]), surfactant structure, and hydrotrope tail length were all investigated. Dispersed water domains were probed using high pressure small-angle neutron scattering (HP-SANS), which provided evidence for elongated reversed micelles in supercritical CO₂. These new micelles have significantly lower fluorination levels than previously reported (6–29 wt % cf. 14–52 wt %), and furthermore, they support higher water dispersion levels than other related systems (<i>w</i> = 15 cf. <i>w</i> = 5). The intrinsic viscosities of these w/c microemulsions were estimated based on micelle aspect ratio; from this value a relative viscosity value can be estimated through combination with the micellar volume fraction (ϕ). Combining these new results with those for all other reported systems, it has been possible to “map” predicted viscosity increases in CO₂ arising from elongated reversed micelles, as a function of surfactant fluorination and micellar aspect ratio

Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

Multihydroxyl end functional polyethylenes have been prepared with controlled molecular weight, microstructure, and functionalization. These materials, designed as interfacially active blend additives for polar interfaces, are thermally stable up to ∼250 °C and to have similar crystallinity and dynamics to their unfunctionalized homo­polymer analogues. The polymers segregated strongly to silicon oxide interfaces, with adsorbed layers forming spontaneously at annealed polymer interfaces, having surface excess concentrations approaching 2<i>R</i>_g and a maximum areal density of approximately 0.6 adsorbed chains per nm². This interfacial activity is achieved almost without detriment to the bulk physical properties of the polymer as evidenced by thermal analysis, quasi-elastic neutron scattering, and small-angle neutron scattering (SANS). SANS experiments show little evidence for aggregation of the dihydroxyl functionalized polymers in blends with PE homopolymers, which is thought to explain why these additives have particularly strong interfacial adsorption, even at relatively high concentrations. A modest level of segregation of the additives to exposed blend surfaces was also seen, particularly when the additive molecular weight was significantly lower than that of the matrix. We attribute this to a combination of the relatively low molecular weight of the additives and the marginally lower surface energy associated with deuterated polymers

Glycerol Solvates DPPC Headgroups and Localizes in the Interfacial Regions of Model Pulmonary Interfaces Altering Bilayer Structure

The inclusion of glycerol in formulations for pulmonary drug delivery may affect the bioavailability of inhaled steroids by retarding their transport across the lung epithelium. The aim of this study was to evaluate whether the molecular interactions of glycerol with model pulmonary interfaces provide a biophysical basis for glycerol modifying inhaled drug transport. Dipalmitoylphosphatidylcholine (DPPC) monolayers and liposomes were used as model pulmonary interfaces, in order to examine the effects of bulk glycerol (0–30% w/w) on their structures and dynamics using complementary biophysical measurements and molecular dynamics (MD) simulations. Glycerol was found to preferentially interact with the carbonyl groups in the interfacial region of DPPC and with phosphate and choline in the headgroup, thus causing an increase in the size of the headgroup solvation shell, as evidenced by an expansion of DPPC monolayers (molecular area increased from 52 to 68 Ų) and bilayers seen in both Langmuir isotherms and MD simulations. Both small angle neutron scattering and MD simulations indicated a reduction in gel phase DPPC bilayer thickness by ∼3 Å in 30% w/w glycerol, a phenomenon consistent with the observation from FTIR data, that glycerol caused the lipid headgroup to remain oriented parallel to the membrane plane in contrast to its more perpendicular conformation adopted in pure water. Furthermore, FTIR measurements suggested that the terminal methyl groups of the DPPC acyl chains were constrained in the presence of glycerol. This observation is supported by MD simulations, which predict bridging between adjacent DPPC headgroups by glycerol as a possible source of its putative membrane stiffening effect. Collectively, these data indicate that glycerol preferentially solvates DPPC headgroups and localizes in specific areas of the interfacial region, resulting in structural changes to DPPC bilayers which may influence cell permeability to drugs

Internal Nanoparticle Structure of Temperature-Responsive Self-Assembled PNIPAM‑<i>b</i>‑PEG‑<i>b</i>‑PNIPAM Triblock Copolymers in Aqueous Solutions: NMR, SANS, and Light Scattering Studies

In this study, we report detailed information on the internal structure of PNIPAM-<i>b</i>-PEG-<i>b</i>-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering, and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-<i>b</i>-PEG-<i>b</i>-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solidlike particles and chain network with a mesh size of 1–3 nm are present, nanoparticles formed from PNIPAM-<i>b</i>-PEG-<i>b</i>-PNIPAM copolymers have nonuniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation

Charging Poly(methyl Methacrylate) Latexes in Nonpolar Solvents: Effect of Particle Concentration

The electrophoresis of a well-established model system of charged colloids in nonpolar solvents has been studied as a function of particle volume fraction at constant surfactant concentration. Dispersions of poly­(12-hydroxystearic acid)-stabilized poly­(methyl methacrylate) (PMMA) latexes in dodecane were prepared with added Aerosol OT surfactant as the charging agent. The electrophoretic mobility (μ) of the PMMA latexes is found to decrease with particle concentration. The particles are charged by a small molecule charging agent (AOT) at finite concentration, and this makes the origin of this decrease in μ unclear. There are two suggested explanations. The decrease could either be due to the reservoir of available surfactant being exhausted at high particle concentrations or the interactions between the charged particles at high particle number concentrations. Contrast-variation small-angle neutron scattering measurements of PMMA latexes and deuterated AOT-<i>d</i>₃₄ surfactant in latex core contrast-matched solvent were used to study the former, and electrokinetic modeling was used to study the latter. As the same amount of AOT-<i>d</i>₃₄ is found to be incorporated with the latexes at all volume fractions, the solvodynamic and electrical interactions between particles are determined to be the explanation for the decrease in mobility. These measurements show that, for small latexes, there are interactions between the charged particles at all accessible particle volume fractions and that it is necessary to account for this to accurately determine the electrokinetic ζ potential

Peptide Self-Assemblies from Unusual α‑Sheet Conformations Based on Alternation of d/l Amino Acids

Peptide self-assembly is a hierarchical process during which secondary structures formed in the initial stages play a critical role in determining the subsequent assembling processes and final structural ordering. Unusual secondary structures hold promise as a source to develop novel supramolecular architectures with unique properties. In this work, we report the design of a new peptide self-assembly strategy based on unusual α-sheet secondary structures. In light of the strong propensity of leucine toward forming helical conformations and its high hydrophobicity, we design two short amphiphilic peptides Ac-LDLLDLK-NH2 and Ac-DLLDLLDK-NH2 with alternating l- and d-form amino acids. Microscopic imaging, neutron scattering, and spectroscopic measurements indicate that the two heterochiral peptides form highly ordered wide nanotubes and helical ribbons with monolayer thickness, in sharp contrast to twisted nanofibrils formed by the homochiral peptide Ac-LLLLK-NH2. Molecular dynamics simulations from monomers to trimers reveal that the two heteropeptides fold into α-sheets instead of β-sheets, which readily pack into tubular architectures in oligomer simulations. Simulated circular dichroism spectra based on α-sheet oligomers validate the proposed α-sheet secondary structures. These results form an important basis for the rational design of higher-order peptide assemblies with novel properties based on unusual α-sheet secondary structures