Yeling Dai

Demonstration of Feasibility of X-Ray Free Electron Laser Studies of Dynamics of Nanoparticles in Entangled Polymer Melts

The recent advent of hard x-ray free electron lasers (XFELs) opens new areas of science due to their exceptional brightness, coherence, and time structure. In principle, such sources enable studies of dynamics of condensed matter systems over times ranging from femtoseconds to seconds. However, the studies of “slow” dynamics in polymeric materials still remain in question due to the characteristics of the XFEL beam and concerns about sample damage. Here we demonstrate the feasibility of measuring the relaxation dynamics of gold nanoparticles suspended in polymer melts using X-ray photon correlation spectroscopy (XPCS), while also monitoring eventual X-ray induced damage. In spite of inherently large pulse-to-pulse intensity and position variations of the XFEL beam, measurements can be realized at slow time scales. The X-ray induced damage and heating are less than initially expected for soft matter materials.

Synchrotron X-ray studies of rapidly evolving morphology of self-assembled nanoparticle films under lateral compression.

Interfacial nanostructures represent a class of systems that are highly relevant to studies of quasi-2D phases, chemical self-assembly, surfactant behavior, and biologically relevant membranes. Previous studies have shown that under lateral compression a Langmuir film of gold (Au) nanoparticles assembled at the liquid-air interface exhibits rich mechanical behavior: it undergoes a rapid structural and morphological evolution from a monolayer to a trilayer via an intermediate hash-like phase. We report the results of studying this structural evolution using grazing incidence X-ray off-specular scattering (GIXOS). We utilize GIXOS to obtain a quantitative mapping of electron density profile normal to the liquid surface with a subnanometer resolution and follow the structural evolution of the Au nanoparticle film under lateral compression with a subminute temporal resolution. As the surface pressure is increased, the self-assembled nanoparticle monolayer first crinkles into a double-layer phase before forming a trilayer. This study reveals the existence of a transient bilayer phase and provides a microscopic picture of the particle-level crinkling phenomena of ultrathin films. These studies were previously impossible due to the relatively short time scales involved in crinkling formation of these transient phases and their intrinsically inhomogeneous nature.

A comparative study of Langmuir surfactant films: Grazing incidence x-ray off-specular scattering vs. x-ray specular reflectivity

Surface monolayers assembled on a liquid sub-phase represent a class of systems that is of great interest for studies of phase transitions in quasi-2D systems, chemical self-assembly, surfactant behavior, and biologically relevant monolayers and membranes. X-ray scattering is ideal for studying structural, dynamic, and mechanical properties of these surface monolayers at nanoscale due to the penetrating ability and short wavelength of x-rays. We show here that grazing incidence x-ray off-specular scattering (GIXOS) provides rapid access to in-plane and out-of-plane nanoscale structure, surface fluctuating modes, and potentially bending stiffness. We show that analysis of GIXOS data is highly sensitive to resolution effects. We further present detailed analysis of GIXOS from phospholipid 1,2-dipalmitoyl-phosphatidyl-choline C40H80NO8P (DPPC) and obtain quantitative, angstrom-resolution details of electron density profile normal to the surface that is comparable to those that are obtained from specular x-ra...

Governing factors in stress response of nanoparticle films on water surface

The mechanical properties of self-assembled silver nanoparticle (Ag-NP) films at the air-liquid interface are studied using both visible light optics and x-ray scattering techniques. The response of such films to compression is compared with results from previously studied gold nanoparticle (Au-NP) films, showing many similarities, along with significant differences. Possible factors governing the stress response of nanoparticle films are discussed.

Novel comparison of microscopy and diffraction techniques on the structure of iron oxide nanoparticle monolayers transferred by Langmuir-Schaefer method

Iron oxide nanoparticles undergo self-assembly into well-ordered monolayer films of macroscopic size at the air-water interface. This self-assembly process is the result of the van der Waals forces between the constituent particles. For roughly spherical particles, this monolayer is a 2D hexagonal close packed lattice. With Grazing Incidence X-Ray Diffraction (GID), one can obtain global statistical information about the films spacing and correlation length. Herein, we demonstrate that comparable structural information can be obtained by a novel Fourier transform analysis method applied to Scanning Electron Microscopy (SEM) images taken of the film after it has been transferred to a silicon substrate. This consists of using numerical methods to isolate the lattice structure of the monolayer in the SEM image to which a 2D discrete Fourier Transform is applied and the result integrated. This results in Bragg peak information akin to that obtained from GID, whose structure shows the same hexagonal close packed lattice with similar spacing and of greater peak contrast. This analysis technique may prove to be a suitable alternative or compliment to GID for many applications.

Liquid Surface X-ray Studies of Gold Nanoparticle–Phospholipid Films at the Air/Water Interface

Amphiphilic phospholipids and nanoparticles functionalized with hydrophobic capping ligands have been extensively investigated for their capacity to self-assemble into Langmuir monolayers at the air/water interface. However, understanding of composite films consisting of both nanoparticles and phospholipids, and by extension, the complex interactions arising between nanomaterials and biological membranes, remains limited. In this work, dodecanethiol-capped gold nanoparticles (Au-NPs) with an average core diameter of 6 nm were incorporated into 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayers with surface densities ranging from 0.1 to 20% area coverage at a surface pressure of 30 mN/m. High resolution liquid surface X-ray scattering studies revealed a phase separation of the DPPC and Au-NP components of the composite film, as confirmed with atomic force microscopy after the film was transferred to a substrate. At low Au-NP content, the structural organization of the phase-separated film is best described as a DPPC film containing isolated islands of Au-NPs. However, increasing the Au-NP content beyond 5% area coverage transforms the structural organization of the composite film to a long-range interconnected network of Au-NP strands surrounding small seas of DPPC, where the density of the Au-NP network increases with increasing Au-NP content. The observed phase separation and structural organization of the phospholipid and nanoparticle components in these Langmuir monolayers are useful for understanding interactions of nanoparticles with biological membranes.