Infection Diagnostics Enabled by Selective Adsorption of Breath-Based Biomarkers in Zr-Based Metal-Organic Frameworks.

Exhaled breath contains trace levels of volatile organic compounds (VOCs) that can reveal information about metabolic processes or pathogens in the body. These molecules can be used for medical diagnosis, but capturing and accurately measuring them is a significant challenge in chemical separations. A highly selective nanoporous sorbent can be used to capture target molecules from a breath sample and preconcentrate them for use in a detector.

Revealing the hidden structure of disordered materials by parameterizing their local structural manifold.

Durable interest in developing a framework for the detailed structure of glassy materials has produced numerous structural descriptors that trade off between general applicability and interpretability. However, none approach the combination of simplicity and wide-ranging predictive power of the lattice-grain-defect framework for crystalline materials. Working from the hypothesis that the local atomic environments of a glassy material are constrained by enthalpy minimization to a low-dimensional manifold in atomic coordinate space, we develop a generalized distance function, the Gaussian Integral Inner Product (GIIP) distance, in connection with agglomerative clustering and diffusion maps, to parameterize that manifold.

Water adsorption on MoS under realistic atmosphere conditions and impacts on tribology.

Molybdenum disulfide (MoS) is a 2D material widely used as a dry lubricant. However, exposure to water and oxygen is known to reduce its effectiveness, and therefore an understanding of the uptake of water is important information for mitigating these effects. Here we use grand canonical Monte Carlo simulations to rigorously study water adsorption on MoS surfaces and edges with different concentrations of defects under realistic atmospheric conditions ( various temperatures and humidity levels).

Interactions of Water with Pristine and Defective MoS.

Molybdenum disulfide (MoS) is a lamellar solid lubricant often used in aerospace applications because of its extremely low friction coefficient (∼0.01) in inert environments. The lubrication performance of MoS is significantly impaired by exposure to even small amounts of water and oxygen, and the mechanisms behind this remain poorly understood.

Formation of Coherent 1H-1T Heterostructures in Single-Layer MoS on Au(111).

Heterojunctions of semiconductors and metals are the fundamental building blocks of modern electronics. Coherent heterostructures between dissimilar materials can be achieved by composition, doping, or heteroepitaxy of chemically different elements. Here, we report the formation of coherent single-layer 1H-1T MoS heterostructures by mechanical exfoliation on Au(111), which are chemically homogeneous with matched lattices but show electronically distinct semiconducting (1H phase) and metallic (1T phase) character, with the formation of these heterojunctions attributed to a combination of lattice strain and charge transfer.

Evidence of Inverse Hall-Petch Behavior and Low Friction and Wear in High Entropy Alloys.

We present evidence of inverse Hall-Petch behavior for a single-phase high entropy alloy (CoCrFeMnNi) in ultra-high vacuum and show that it is associated with low friction coefficients (~0.3). Grain size measurements by STEM validate a recently proposed dynamic amorphization model that accurately predicts grain size-dependent shear strength in the inverse Hall-Petch regime.

Ultimate Strength of Metals.

We present a theoretical model that predicts the peak strength of polycrystalline metals based on the activation energy (or stress) required to cause deformation via amorphization. Building on extensive earlier work, this model is based purely on materials properties, requires no adjustable parameters, and is shown to accurately predict the strength of four exemplar metals (fcc, bcc, and hcp, and an alloy). This framework reveals new routes for design of more complex high-strength materials systems, such as compositionally complex alloys, multiphase systems, nonmetals, and composite structures.

New nanoscale toughening mechanisms mitigate embrittlement in binary nanocrystalline alloys.

Nanocrystalline metals offer significant improvements in structural performance over conventional alloys. However, their performance is limited by grain boundary instability and limited ductility. Solute segregation has been proposed as a stabilization mechanism, however the solute atoms can embrittle grain boundaries and further degrade the toughness.

Achieving Ultralow Wear with Stable Nanocrystalline Metals.

Recent work suggests that thermally stable nanocrystallinity in metals is achievable in several binary alloys by modifying grain boundary energies via solute segregation. The remarkable thermal stability of these alloys has been demonstrated in recent reports, with many alloys exhibiting negligible grain growth during prolonged exposure to near-melting temperatures. Pt-Au, a proposed stable alloy consisting of two noble metals, is shown to exhibit extraordinary resistance to wear.

Impact of Microstructure on MoS Oxidation and Friction.

This work demonstrates the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS). We report on systematic investigations of oxidation and friction for two MoS films with distinctively different microstructures-amorphous and planar/highly-ordered-before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials.

Molecular scale modeling of polymer imprint nanolithography.

We present the results of large-scale molecular dynamics simulations of two different nanolithographic processes, step-flash imprint lithography (SFIL), and hot embossing. We insert rigid stamps into an entangled bead-spring polymer melt above the glass transition temperature. After equilibration, the polymer is then hardened in one of two ways, depending on the specific process to be modeled.

Forces between functionalized silica nanoparticles in solution.

To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5-nm-diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface.

Molecular dynamics simulations of water confined between matched pairs of hydrophobic and hydrophilic self-assembled monolayers.

We have conducted a molecular dynamics (MD) simulation study of water confined between methyl-terminated and carboxyl-terminated alkylsilane self-assembled monolayers (SAMs) on amorphous silica substrates. In doing so, we have investigated the dynamic and structural behavior of the water molecules when compressed to loads ranging from 20 to 950 MPa for two different amounts of water (27 and 58 water molecules/nm2). Within the studied range of loads, we observe that no water molecules penetrate the hydrophobic region of the carboxyl-terminated SAMs.

Water in nanoconfinement between hydrophilic self-assembled monolayers.

Molecular dynamics (MD) simulations of water confined to subnanometer thicknesses between carboxyl-terminated alkanethiol self-assembled monolayers (SAMs) on gold were performed to address conflicts in the literature on the structure and response of water in confinement. The amount of water was varied to yield submonolayer to bilayer structures. The orientation of the water is affected by the confinement, especially in the submonolayer case.

Water penetration of damaged self-assembled monolayers.

The interaction of water with self-assembled monolayers (SAMs) on amorphous silica is investigated using classical molecular dynamics simulation. Damage is induced through shear simulations with model atomic force microscopy (AFM) tips and separately with controlled extraction. We find that SAM coatings that have been slightly damaged (by normal loads close to 10 nN from a 10-nm-diameter AFM tip) are susceptible to water penetration and migration to the underlying hydrophilic substrate.

Simulations of nanotribology with realistic probe tip models.

We present the results of massively parallel molecular dynamics simulations aimed at understanding the nanotribological properties of alkylsilane self-assembled monolayers (SAMs) on amorphous silica. In contrast to studies with opposing flat plates, as found in the bulk of the simulation literature, we use a model system with a realistic AFM tip (radius of curvature ranging from 3 to 30 nm) in contact with a SAM-coated silica substrate. We compare the differences in response between systems in which chains are fully physisorbed, fully chemisorbed, and systems with a mixture of the two.

Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields.

We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins.

Tribological properties of alkylsilane self-assembled monolayers.

In this study, we perform molecular dynamics simulations of adhesive contact and friction between alkylsilane Si(OH)(3)(CX(2))(10)CX(3) and alkoxylsilane Si(OH)(2)(CX(2))(10)CX(3) (where X = H or F) self-assembled monolayers (SAMs) on an amorphous silica substrate. The alkylsilane SAMs are primarily hydrogen-bonded or physisorbed to the surface. The alkoxylsilane SAMs are covalently bonded or chemisorbed to the surface.

Systematic study of the effect of disorder on nanotribology of self-assembled monolayers.

The adhesion and friction between pairs of ordered and disordered self-assembled monolayers on SiO2 are studied using molecular dynamics. The disorder is introduced by randomly removing chains from a well ordered crystalline substrate and by attaching chains to an amorphous substrate. The adhesion force between monolayers at a given separation increases monotonically with chain length at full coverage and with coverage for fixed chain length.

Frictional dynamics of fluorine-terminated alkanethiol self-assembled monolayers.

The frictional dynamics of fluorine-terminated alkanethiol (S(CH2)8CF3) self-assembled monolayers (SAMs) on gold are studied using molecular dynamics simulations. The simulations treat the interactions between two SAMs on flat surfaces. The structure and frictional behavior are investigated as a function of applied pressure (200 MPa to 1 GPa) for a shear velocity of 2 m/s and compared to methyl-terminated alkanethiol SAMs.