arXiv subjects

Michael S. Strano

Publications and source records attributed to Michael S. Strano.

11 recordsLinked to original sources

arXiv2026

Molecularly Thin Polyaramid Nanomechanical Resonators

Two-dimensional polyaramids exhibit strong hydrogen bonding to create molecularly thin nanosheets analogous to graphene. Here, we report the first nanomechanical resonators made out of a two-dimensional polyaramid, 2DPA-1, with thicknesses as small as 8 nm. To fabricate these molecular-scale resonators, we transferred nanofilms of 2DPA-1 onto chips with previously etched arrays of circular microwells. We then characterized the thermal resonances of these resonators under different conditions. When there is no residual gas inside the 2DPA-1-covered microwells, the eigenfrequencies are well-described by a tensioned plate theory, providing the Young's modulus and tension of the 2DPA-1 nanofilms. With gas present, the nanofilms bulge up and mechanical resonances are modified due to the adhesion, bulging and slack present in the system. The fabrication and mechanical characterization of these first 2DPA-1 nanomechanical resonators represent a convincing path toward molecular-scale polymeric NEMS with high mechanical strength, low density, and synthetic processability.

cond-mat.mes-hall↗

arXiv2024

Hydrogen bonding in water under extreme confinement

Fluids under extreme confinement exhibit unique structures and intermolecular bonding, distinct from their bulk analogs, driving innovative applications at the water-energy nexus. Probing confined water experimentally at the length scale of intermolecular and surface forces has, however, remained a challenge. Here, we report direct molecular-level observations of hydrogen bonding in water confined inside individual carbon nanotubes, enabled by in-situ vibrational electron energy-loss spectroscopy with nanoscale resolution. Hydrogen bonding is probed via the intramolecular O-H stretching frequency, which serves as a sensitive spectral signature of the local intermolecular bonding environment. Water in larger carbon nanotubes exhibit the bonded O-H vibrations of bulk water, but at smaller diameters, the frequency blueshifts to near the free O-H stretch found in water vapor and hydrophobic surfaces, indicating a highly dispersed, non-H-bonded environment. Theoretical analysis based on quantum vibrational oscillators indicates that enhanced damping rates, corresponding to rapid hydrogen-bond fluctuations, leads the bimodal spectral peaks to merge into a single broad feature, matching the experimental observation. Furthermore, cryogenic experiments provide insights into complex structural phase transitions of confined water. This research reveals the quantum and dynamic nature of hydrogen bonds under confinement and the potential impact of unveiling molecular-level structure and bonding in confined fluids.

physics.chem-ph↗

arXiv2022

Emergent Microrobotic Oscillators via Asymmetry-Induced Order

Spontaneous low-frequency oscillations on the order of several hertz are the drivers of many crucial processes in nature. From bacterial swimming to mammal gaits, the conversion of static energy inputs into slowly oscillating electrical and mechanical power is key to the autonomy of organisms across scales. However, the fabrication of slow artificial oscillators at micrometre scales remains a major roadblock towards the development of fully-autonomous microrobots. Here, we report the emergence of a low-frequency relaxation oscillator from a simple collective of active microparticles interacting at the air-liquid interface of a peroxide drop. Their collective oscillations form chemomechanical and electrochemical limit cycles that enable the transduction of ambient chemical energy into periodic mechanical motion and on-board electrical currents. Surprisingly, the collective can oscillate robustly even as more particles are introduced, but only when we add a single particle with modified reactivity to intentionally break the system's permutation symmetry. We explain such emergent order through a novel thermodynamic mechanism for asymmetry-induced order. The energy harvested from the stabilized system oscillations enables the use of on-board electronic components, which we demonstrate by cyclically and synchronously driving microrobotic arms. This work highlights a new strategy for achieving low-frequency oscillations at the microscale that are otherwise difficult to observe outside of natural systems, paving the way for future microrobotic autonomy.

nlin.AO↗

arXiv2021

Thermally Fluctuating, Semiflexible Sheets in Simple Shear Flow

We perform Brownian dynamics simulations of semiflexible colloidal sheets with hydrodynamic interactions and thermal fluctuations in shear flow. As a function of the ratio of bending rigidity to shear energy (a dimensionless quantity we denote $S$) and the ratio of bending rigidity to thermal energy, we observe a dynamical transition from stochastic flipping to crumpling and continuous tumbling. This dynamical transition is broadened by thermal fluctuations, and the value of $S$ at which it occurs is consistent with the onset of chaotic dynamics found for athermal sheets. The effects of different dynamical conformations on rheological properties such as viscosity and normal stress differences are also quantified. Namely, the viscosity in a dilute dispersion of sheets is found to decrease with increasing shear rate (shear-thinning) up until the dynamical crumpling transition, at which point it increases again (shear-thickening), and non-zero first normal stress differences are found that exhibit a local maximum with respect to temperature at large $S$ (small shear rate). These results shed light on the dynamical behavior of fluctuating 2D materials dispersed in fluids and should greatly inform the design of associated solution processing methods.

cond-mat.soft↗

arXiv2021

Buckling, Crumpling, and Tumbling of Semiflexible Sheets in Simple Shear Flow

As 2D materials such as graphene, transition metal dichalcogenides, and 2D polymers become more prevalent, solution processing and colloidal-state properties are being exploited to create advanced and functional materials. However, our understanding of the fundamental behavior of 2D sheets and membranes in fluid flow is still lacking. In this work, we perform numerical simulations of athermal semiflexible sheets with hydrodynamic interactions in shear flow. For sheets initially oriented in the flow-gradient plane, we find buckling instabilities of different mode numbers that vary with bending stiffness and can be understood with a quasi-static model of elasticity. For different initial orientations, chaotic tumbling trajectories are observed. Notably, we find that sheets fold or crumple before tumbling but do not stretch again upon applying greater shear.

cond-mat.soft↗

arXiv2021

An Irreversible Synthetic Route to an Ultra-Strong Two-Dimensional Polymer

Polymers that extend covalently in two dimensions have attracted recent attention as a means of combining the mechanical strength and in-plane energy conduction of conventional two-dimensional (2D) materials with the low densities, synthetic processability, and organic composition of their one-dimensional counterparts. Efforts to date have proven successful in forms that do not allow full realization of these properties, such as polymerization at flat interfaces or fixation of monomers in immobilized lattices. A frequently employed synthetic approach is to introduce microscopic reversibility, at the cost of bond stability, to achieve 2D crystals after extensive error correction. Herein we demonstrate a synthetic route to 2D irreversible polycondensation directly in the solution phase, resulting in covalently bonded 2D polymer platelets that are chemically stable and highly processable. Further fabrication offers highly oriented, free-standing films which exhibit exceptional 2D elastic modulus and yield strength at 50.9 +- 15.0 GPa and 0.976 +- 0.113 GPa, respectively. Platelet alignment is evidenced by polarized photoluminescence centered at 580 and 680 nm from different dipole transitions. This new synthetic route provides opportunities for 2D polymers in applications ranging from composite structures to molecular sieving membranes.

cond-mat.soft↗

arXiv2020

A Virucidal Face Mask Based on the Reverse-flow Reactor Concept for Thermal Inactivation of SARS-CoV-2

While facial coverings over the nose and mouth reduce the spread of the virus SARS-CoV-2 by filtration, masks capable of viral inactivation by heating could provide a complementary method to limit viral transmission. In this work, we introduce a new virucidal face mask concept based on a reverse-flow reactor driven by the oscillatory flow of human breath. The governing heat and mass transport equation are formulated and solved to analyze designs that evaluate both viral and CO2 transport during inhalation and exhalation. Given limits imposed by the volume and frequency of human breath, the kinetics of SARS-CoV-2 thermal inactivation, and human safety and comfort, heated masks may inactivate SARS-CoV-2 in inflow and outflow to medical grade sterility. We detail one particular design, with a volume of 300 mL at 90 $^\circ$C, that achieves a 3-log reduction in viral load with minimal viral impedance within the mask mesh, with partition coefficient around 2. This study is the first quantitative analysis of virucidal thermal inactivation within a protective face mask and addresses a pressing need for new approaches for personal protective equipment during a global pandemic.

physics.flu-dyn↗

arXiv2019

Observation and Spectral Assignment of a Family of Hexagonal Boron Nitride Lattice Defects

Atomic vacancy defects in single unit cell thick hexagonal boron nitride are of significant interest because of their photophysical properties, including single-photon emission, and promising applications in quantum communication and computation. The spectroscopic assignment of emission energies to specific atomic vacancies within the triangular lattice is confounded by the exponential scaling of defect candidates with the number of removed atoms. Herein, we collect more than 1000 spectra consisting of single, isolated zero-phonon lines between 1.69 and 2.25 eV, observing 6 quantized zero-phonon lines arising from hexagonal boron nitride vacancies. A newly developed computational framework for isomer cataloguing significantly narrows the number of candidate vacancies. Direct lattice imaging of hexagonal boron nitride, electronic structure calculations, and subsequent boric acid etching are used to definitively assign the 6 features. Systematic chemical etching supports the assignment by demonstrating the sequence of growth of successively larger vacancy centres from smaller ones, with the defects including a single B vacancy and a 16-atom triangular defect. These features exhibit a range of emission lifetimes from 1 to 6 ns, and phonon sidebands offset by the dominant lattice phonon in hexagonal boron nitride near 1370 cm-1. This assignment should significantly advance the solid-state chemistry and photophysics of such vacancy emitters.

cond-mat.mtrl-sci↗

arXiv2015

Molecular Valves for Controlling Gas Phase Transport Made from Discrete Angstrom-Sized Pores in Graphene

An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid state nanopores.

cond-mat.mes-hall↗

arXiv2012

Chemical reactivity imprint lithography on graphene: Controlling the substrate influence on electron transfer reactions

The chemical functionalization of graphene enables control over electronic properties and sensor recognition sites. However, its study is confounded by an unusually strong influence of the underlying substrate. In this paper, we show a stark difference in the rate of electron transfer chemistry with aryl diazonium salts on monolayer graphene supported on a broad range of substrates. Reactions proceed rapidly when graphene is on SiO_2 and Al_2O_3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces. The effect is contrary to expectations based on doping levels and can instead be described using a reactivity model accounting for substrate-induced electron-hole puddles in graphene. Raman spectroscopic mapping is used to characterize the effect of the substrates on graphene. Reactivity imprint lithography (RIL) is demonstrated as a technique for spatially patterning chemical groups on graphene by patterning the underlying substrate, and is applied to the covalent tethering of proteins on graphene.

cond-mat.mtrl-sci↗

arXiv2005

Direct Experimental Evidence of Exciton-Phonon Bound States in Carbon Nanotubes

We present direct experimental observation of exciton-phonon bound states in the photoluminescence excitation spectra of isolated single walled carbon nanotubes in aqueous suspension. The photoluminescence excitation spectra from several distinct single-walled carbon nanotubes show the presence of at least one sideband related to the tangential modes, lying {200 meV} above the main absorption/emission peak. Both the energy position and line shapes of the sidebands are in excellent agreement with recent calculations [PRL {\bf 94},027402 (2005)] that predict the existence of exciton-phonon bound states, a sizable spectral weight transfer to these exciton-phonon complexes and that the amount of this transfer depends on the specific nanotube structure and diameter. The observation of these novel exciton-phonon complexes is a strong indication that the optical properties of carbon nanotubes have an excitonic nature and also of the central role played by phonons in describing the excitation and recombination mechanisms in carbon nanotubes.

cond-mat.mtrl-sci↗