Mati Meron

Applying the Bootstrap to Taxometric Analysis: Generating Empirical Sampling Distributions to Help Interpret Results

Meehls taxometric method was developed to distinguish categorical and continuous constructs. However, taxometric output can be difficult to interpret because expected results for realistic data conditions and differing procedural implementations have not been derived analytically or studied through rigorous simulations. By applying bootstrap methodology, one can generate empirical sampling distributions of taxometric results using data–based estimates of relevant population parameters. We present iterative algorithms for creating bootstrap samples of taxonic and dimensional comparison data that reproduce important features of the research data with good precision and negligible bias. In a series of studies, we demonstrate the utility of these comparison data as an interpretive aid in taxometric research. Strengths and limitations of the approach are discussed along with directions for future research.

Surface Crystallization in a Liquid AuSi Alloy

X-ray measurements reveal a crystalline monolayer at the surface of the eutectic liquid Au82Si18, at temperatures above the alloys melting point. Surface-induced atomic layering, the hallmark of liquid metals, is also found below the crystalline monolayer. The layering depth, however, is threefold greater than that of all liquid metals studied to date. The crystallinity of the surface monolayer is notable, considering that AuSi does not form stable bulk crystalline phases at any concentration and temperature and that no crystalline surface phase has been detected thus far in any pure liquid metal or nondilute alloy. These results are discussed in relation to recently suggested models of amorphous alloys.

From random walk to single-file diffusion.

We report an experimental study of diffusion in a quasi-one-dimensional (q1D) colloid suspension which behaves like a Tonks gas. The mean squared displacement as a function of time is described well with an ansatz encompassing a time regime that is both shorter and longer than the mean time between collisions. The ansatz asserts that the inverse mean squared displacement is the sum of the inverse mean squared displacement for short time normal diffusion (random walk) and the inverse mean squared displacement for asymptotic single-file diffusion (SFD). The dependence of the 1D mobility in the SFD on the concentration of the colloids agrees quantitatively with that derived for a hard rod model, which confirms for the first time the validity of the hard rod SFD theory. We also show that a recent SFD theory by Kollmann leads to the hard rod SFD theory for a Tonks gas.

A synchrotron x-ray liquid surface spectrometer

The design of a synchrotron x-ray liquid surface spectrometer at beamline X19C at the National Synchrotron Light Source is described. This spectrometer is capable of performing the full range of x-ray surface scattering techniques. A few examples of measurements made using this spectrometer are presented, including studies of organic monolayers on the surface of water and of the structure of strongly fluctuating oil–microemulsion interfaces. The measurements discussed illustrate the accuracy, resolution, and capabilities of the spectrometer.

Tuning ion correlations at an electrified soft interface

Ion distributions play a central role in various settings—from biology, where they mediate the electrostatic interactions between charged biomolecules in solution, to energy storage devices, where they influence the charging properties of supercapacitors. These distributions are determined by interactions dictated by the chemical properties of the ions and their environment as well as the long-range nature of the electrostatic force. Recent theoretical and computational studies have explored the role of correlations between ions, which have been suggested to underlie a number of counterintuitive results, such as like-charge attraction. However, the interdependency between ion correlations and other interactions that ions experience in solution complicates the connection between physical models of ion correlations and the experimental investigation of ion distributions. We exploit the properties of the liquid/liquid interface to vary the coupling strength of ion–ion correlations from weak to strong while monitoring their influence on ion distributions at the nanometer scale with X-ray reflectivity and the macroscopic scale with interfacial tension measurements. These data are in agreement with the predictions of a parameter-free density functional theory that includes ion–ion correlations and ion–solvent interactions over the entire range of experimentally tunable correlation coupling strengths (from 0.8 to 3.7). This study provides evidence for a sharply defined electrical double layer for large coupling strengths in contrast to the diffuse distributions predicted by mean field theory, thereby confirming a common prediction of many ion correlation models. The reported findings represent a significant advance in elucidating the nature and role of ion correlations in charged soft matter.

Atomic-Scale Surface Demixing in a Eutectic Liquid BiSn Alloy

Resonant x-ray reflectivity of the surface of the liquid phase of the Bi(43)Sn(57) eutectic alloy reveals atomic-scale demixing extending over three near-surface atomic layers. Because of the absence of an underlying atomic lattice which typically defines adsorption in crystalline alloys, studies of adsorption in liquid alloys provide unique insight on interatomic interactions at the surface. The observed composition modulation could be accounted for quantitatively by the Defay-Prigogine and Strohl-King multilayer extensions of the single-layer Gibbs model, revealing a near-surface domination of the attractive Bi-Sn interaction over the entropy.

Anomalous layering at the liquid sn surface

X-ray reflectivity measurements on the free surface of liquid Sn are presented. They exhibit the high-angle peak, indicative of surface-induced layering, also found for other pure liquid metals (Hg, Ga, and In). However, a low-angle shoulder, not hitherto observed for any pure liquid metal, is also found, indicating the presence of a high-density surface layer. Fluorescence and resonant reflectivity measurements rule out the assignment of this layer to surface segregation of impurities. The reflectivity is modeled well by a 10% contraction of the spacing between the first and second atomic surface layers, relative to that of subsequent layers. Possible reasons for this are discussed.

Molecular Structure of Interfacial Human Meibum Films

Meibum is the primary component of the tear film lipid layer. Thought to play a role in tear film stabilization, understanding the physical properties of meibum and how they change with disease will be valuable in identifying dry eye treatment targets. Grazing incidence X-ray diffraction and X-ray reflectivity were applied to meibum films at an air-water interface to identify molecular organization. At room temperature, interfacial meibum films formed two coexisting scattering phases with rectangular lattices and next-nearest neighbor tilts, similar to the Ov phase previously identified in fatty acids. The intensity of the diffraction peaks increased with compression, although the lattice spacing and molecular tilt angle remained constant. Reflectivity measurements at surface pressures of 18 mN/m and above revealed multilayers with d-spacings of 50 Å, suggesting that vertical organization rather than lateral was predominantly affected by meibum-film compression.

Role of the conformational rigidity in the design of biomimetic antimicrobial compounds.

A link between structural flexibility of biomimetic antimicrobials and their ability to penetrate into the hydrophobic core and disrupt the integrity of bacterial lipid model membranes has been established using liquid surface X-ray scattering techniques. Results indicate that the modes of interaction of flexible and conformationally restrained antimicrobials with the bacterial membranes are different.

The liquid surface/interface spectrometer at ChemMatCARS synchrotron facility at the Advanced Photon Source

We discuss results from the first experiments on a new liquid surface/interface X-ray spectrometer recently commissioned by ChemMatCARS at Sector 15 of the Advanced Photon Source. These experiments include studies of liquid/liquid interfaces, monolayers supported on the water surface, and liquid metal surfaces.