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-d34 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-d34 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.

The effects of counterion exchange on charge stabilization for anionic surfactants in nonpolar solvents.

HYPOTHESIS: Sodium dioctylsulfosuccinate (Aerosol OT or NaAOT) is a well-studied charging agent for model poly(methyl methacrylate) (PMMA) latexes dispersed in nonpolar alkane solvents. Despite this, few controlled variations have been made to the molecular structure. A series of counterion-exchanged analogs of NaAOT with other alkali metals (lithium, potassium, rubidium, and cesium) were prepared, and it was expected that this should influence the stabilization of charge on PMMA latexes and the properties of the inverse micelles. EXPERIMENTS: The electrophoretic mobilities of PMMA latexes were measured for all the counterion-exchanged AOT analogs, and these values were used to calculate the electrokinetic or ζ potentials. This enabled a comparison of the efficacy of the different surfactants as charging agents. Small-angle scattering measurements (using neutrons and X-rays) were performed to determine the structure of the inverse micelles, and electrical conductivity measurements were performed to determine the ionized fractions and Debye lengths. FINDINGS: Sodium AOT is a much more effective charging agent than any of the other alkali metal AOTs. Despite this, the inverse micelle size and electrical conductivity of NaAOT are unremarkable. This shows a significant non-periodicity in the charging efficiency of these surfactants, and it emphasizes that charging particles in nonpolar solvents is a complex phenomenon.

Sulfosuccinate and Sulfocarballylate Surfactants As Charge Control Additives in Nonpolar Solvents.

A series of eight sodium sulfonic acid surfactants with differently branched tails (four double-chain sulfosuccinates and four triple-chain sulfocarballylates) were studied as charging agents for sterically stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane. Tail branching was found to have no significant effect on the electrophoretic mobility of the latexes, but the number of tails was found to influence the electrophoretic mobility. Triple-chain, sulfocarballylate surfactants were found to be more effective. Several possible origins of this observation were explored by comparing sodium dioctylsulfosuccinate (AOT1) and sodium trioctylsulfocarballylate (TC1) using identical approaches: the inverse micelle size, the propensity for ion dissociation, the electrical conductivity, the electrokinetic or ζ potential, and contrast-variation small-angle neutron scattering. The most likely origin of the increased ability of TC1 to charge PMMA latexes is a larger number of inverse micelles. These experiments demonstrate a small molecular variation that can be made to influence the ability of surfactants to charge particles in nonpolar solvents, and modifying molecular structure is a promising approach to developing more effective charging agents.

Charging Dynamics of Aerosol OT Inverse Micelles.

Aerosol OT (AOT) is a commonly used surfactant and charging agent in nonpolar liquids. Properties such as the conductivity of AOT suspensions in nonpolar liquids and the behavior of charged AOT inverse micelles at interfaces have been studied recently, but still little is known about the generation dynamics of charged AOT inverse micelles. In this article, the generation dynamics of charged AOT inverse micelles in dodecane are investigated with transient current measurements. At low applied voltages, the generation rate is sufficiently fast to maintain the equilibrium concentration of charged inverse micelles, such that the current scales proportionally with the applied voltage. However, above a threshold voltage the current becomes limited by the generation of charged inverse micelles. Al2O3-coated electrodes are used to achieve these high-voltage current measurements while reducing surface generation currents. The dependency of the resulting generation-limited currents with the micelle concentration and the liquid volume is compatible with a bulk disproportionation mechanism. The measured currents are analyzed using a model based on drift, generation, and recombination of charged inverse micelles and the corresponding generation and recombination rates of charged AOT inverse micelles have been determined.

Investigation of various types of inverse micelles in nonpolar liquids using transient current measurements.

Transient current measurements are used to characterize a wide variety of charge carriers in nonpolar liquids. The transient current method allows us to obtain both the concentration and mobility of charge carriers and therefore also the hydrodynamic radius using Stokes' law. In this article, five different surfactants in dodecane are investigated: OLOA11K, Solsperse13940, Span80, Span85, and AOT. We show that different types of currents are observed depending on the size of the inverse micelles. For large inverse micelles such as for OLOA11K, Solsperse13940, and Span80, the measurement of the transient current is straightforward because of the low steady-state current level. However, for small inverse micelles such as AOT and Span85, the current from the generation of charges is much larger such that high voltages, a small distance between the electrodes, and dielectric coatings on the electrodes are required to measure the signal related to the initially present charged inverse micelles. The estimated hydrodynamic radii of AOT and Span85, the two smallest inverse micelles, are in good agreement with the values reported in the literature. The comparison of the transient currents with simulations indicates that the dynamics of the charge transport are well-understood.

Interaction between surfactants and colloidal latexes in nonpolar solvents studied using contrast-variation small-angle neutron scattering.

The interaction between deuterium-labeled Aerosol OT surfactant (AOT-d34) and sterically stabilized poly(methyl methacrylate) (PMMA) latex particles dispersed in nonpolar solvents has been studied using contrast-variation small-angle neutron scattering (CV-SANS). The electrophoretic mobilities (µ) of the latexes have been measured by phase-analysis light scattering, indicating that µ is negative. Two analogues of the stabilizers for the particles have been studied as free polymers in the absence of PMMA latexes: poly(12-hydroxystearic acid) (PHSA) polyester and poly(methyl methacrylate)-graft-poly(12-hydroxystearic acid) (PMMA-graft-PHSA) stabilizer copolymer. The scattering from both PHSA in dodecane and PMMA-graft-PHSA in toluene is consistent with extended polymer chains in good solvents. In dodecane, PMMA-graft-PHSA forms polymer micelles, and SANS is consistent with ellipsoidal aggregates formed of around 50 polymer chains. CV-SANS measurements were performed by measuring SANS from systems of PHSA, PMMA-graft-PHSA, and PMMA latexes with 10 and 100 mM surfactant solutions of AOT-d34 in both polymer/particle and AOT contrast-matched solvent. No excess scattering above the polymer or surfactant was found for PHSA in dodecane or PMMA-graft-PHSA in dodecane and toluene. This indicates that AOT does not significantly interact with the free polymers. Excess scattering was observed for systems with AOT-d34 and PMMA latexes dispersed in particle contrast-matched dodecane, consistent with the penetration of AOT into the PMMA latexes. This indicates that AOT does not interact preferentially with the stabilizing layers but, rather, is present throughout the colloids. Previous research ( Langmuir 2010, 26, 6967-6976 ) suggests that AOT surfactant is located in the latex PHSA-stabilizer layer, but all the results in this study are consistent with AOT poorly interacting with alkyl-stabilizer polymers.

Phylogenetic analyses of Coprinopsis sections Lanatuli and Atramentarii identify multiple species within morphologically defined taxa.

Sections Lanatuli and Atramentarii of the genus Coprinopsis contain some of the best known and most important agaric species, including C. cinerea and C. lagopus, yet a critical, phylogeny-based assessment of the species limits has not been carried out. Taxa have been characterized chiefly on the basis of morphological characters, which however show little discriminatory power and/or considerable overlap between several species pairs. We used ITS and LSU sequence data of 29 described taxa in Coprinopsis sections Lanatuli and Atramentarii to infer species limits and the correspondence between morphological characters and species lineages, as well as to examine the phylogenetic affinities of sections Lanatuli and Atramentarii. Our analyses recovered three large clades, implying a paraphyly for section Lanatuli. Based on morphology and clade structure, we estimate ca. 38 species in the two sections, including several potentially new taxa, three of which are described herein. Coprinopsis pachyderma, C. lagopus var. vacillans, C. acuminata, C. spelaiophila, Coprinus citrinovelatus and Cop. brunneistrangulatus were found to be synonymous with other, earlier described species. Congruent with previous mating studies, our analyses recovered multiple, morphologically indistinguishable lineages within C. lagopus, which included C. lagopus var. vacillans, an ephemeral, developmental variant. Morphological traits supporting the inferred clade structure are discussed. Three new taxa (C. fusispora, C. babosiae, C. villosa), and one new combination (C. mitraespora) are proposed.

Homeland security in the USA: past, present, and future.

This paper examines the evolving and dynamic field of homeland security in the USA. Included in this analysis is the evolution of the creation of the Department of Homeland Security, an overview of the National Warning System, a summary of citizen support groups, and how the field of homeland security has had an impact on the location and architecture of public buildings and facilities. Also included are website directories of citizen support groups and federal agencies related to the field of homeland security.

Transport of charged Aerosol OT inverse micelles in nonpolar liquids.

Surfactants such as Aerosol OT (AOT) are commonly used to stabilize and electrically charge nonpolar colloids in devices such as electronic ink displays. The electrical behavior of such devices is strongly influenced by the presence of charged inverse micelles, formed by excess surfactant that does not cover the particles. The presence of charged inverse micelles results in increased conductivity of the solution, affecting both the energy consumption of the device and its switching characteristics. In this work, we use transient current measurements to investigate the electrical properties of suspensions of the surfactant Aerosol OT in dodecane. No particles are added, to isolate the effect of excess surfactant. The measured currents upon application of a voltage step are found to be exponentially decaying, and can be described by an analytical model based on an equivalent electric circuit. This behavior is physically interpreted, first by the high generation rate of charged inverse micelles giving the suspension resistor like properties, and second by the buildup of layers of charged inverse micelles at both electrodes, acting as capacitors. The model explains the measurements over a large range of surfactant concentrations, applied voltages, and device thicknesses.

Nanoparticle charge control in nonpolar liquids: insights from small-angle neutron scattering and microelectrophoresis.

Electrostatic forces are typically produced in low polarity solvents by the addition of surfactants or charge-control additives. Although widely used, there is no consensus on the mechanism by which surfactants control the level of particle charge. We report an investigation using highly sensitive, single particle optical microelectrophoresis measurements combined with a small-angle neutron scattering study to establish the mechanism of charging by the surfactant AOT in the nonpolar solvent n-dodecane. We show that polymer-grafted particles with no chemically bound surface charges only charge above the critical micellar concentration of the surfactant. The surface potential increases gradually with increasing surfactant concentration c, before finally saturating at high c. The increase in the surface potential is correlated to the amount of surfactant adsorbed onto the surface of the particle. Using deuterated AOT and contrast variation techniques, we demonstrate that the surfactant is adsorbed within the polymer layer surrounding the particle core, probably as individual molecules rather than surfactant aggregates. A simple thermodynamic model accounts for the concentration dependence of the observed surface potential.

Electrostatic charging of nonpolar colloids by reverse micelles.

Colloids dispersed in a nonpolar solvent become charged when reverse micelles are added. We study the charge of individual sterically stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)2], and a copolymer of poly(12-hydroxystearic acid)-poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)2, negative for AOT, and essentially neutral for PHSA-PMMA, the different micellar systems display a number of common features. In particular, we demonstrate that over a wide range of concentrations the particle potential is a constant, independent of the number of micelles added and independent of the colloid size. A simple thermodynamic model, in which the particle charge is generated by the competitive adsorption of both positive and negative micelles, is in good agreement with the experimental data.

Detection of lung cancer by automated sputum cytometry.

INTRODUCTION: Biomarkers may prove to be valuable tools to manage those at risk of lung cancer. Sputum analysis using DNA cytometry has shown promise, but an automated, objective sputum analysis test has yet to be developed. This study evaluated the performance characteristics of the LungSign test for lung cancer and compared them to conventional cytology METHODS: A multicenter validation trial was conducted in which sputum specimens were prospectively collected from subjects suspected of having lung cancer during diagnostic workup. Specimens were placed on slides, DNA stained using Feulgen thionin, and analyzed using an automated cytometry-based scoring system. Smears were also prepared from the sputum specimens, stained by the Papanicolaou procedure, and analyzed using conventional cytology. LungSign scores and conventional cytology results were compared with the subject diagnoses. RESULTS: A total of 1235 high-risk subjects were enrolled at nine clinical sites. Of 1123 subjects included for analysis, 370 were found to have lung cancer--a 33% prevalence. The a priori selected LungSign score threshold detected 40% of all lung cancers and 35% of stage I lung cancers with 91% specificity. Test performance was statistically equivalent across cancer stages, histologic types, and localizations for 330 analyzable lung cancer subjects. LungSign receiver operating characteristic area under the curve measure for the test was 0.692. Conventional cytology detected 16% of lung cancers with 99% specificity. CONCLUSIONS: DNA cytometry of sputum using the LungSign test detects stage I lung cancer and may provide a new tool to manage high-risk individuals.