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Shear of a Coulombic crystal, due to repetitive collisions with its container upon shaking, simultaneously orders and melts the crystal.

The problem this paper addresses is the origin of the hysteretic behavior in two-terminal molecular junctions made from an EGaIn electrode and self-assembled monolayers of alkanethiolates terminated in chelates (transition metal dichlorides complexed with 2,2'-bipyridine; BIPY-MCl

This review focuses on experimental work on nonlinear phenomena in microfluidics, which for the most part are phenomena for which the velocity of a fluid flowing through a microfluidic channel does not scale proportionately with the pressure drop. Examples include oscillations, flow-switching behaviors, and bifurcations. These phenomena are qualitatively distinct from laminar, diffusion-limited flows that are often associated with microfluidics. We explore the nonlinear behaviors of bubbles or droplets when they travel alone or in trains through a microfluidic network or when they assemble into either one- or two-dimensional crystals. We consider the nonlinearities that can be induced by the geometry of channels, such as their curvature or the bas-relief patterning of their base. By casting posts, barriers, or membranes─situated inside channels─from stimuli-responsive or flexible materials, the shape, size, or configuration of these elements can be altered by flowing fluids, which may enable autonomous flow control. We also highlight some of the nonlinearities that arise from operating devices at intermediate Reynolds numbers or from using non-Newtonian fluids or liquid metals. We include a brief discussion of relevant practical applications, including flow gating, mixing, and particle separations.

In soft devices, complex actuation sequences and precise force control typically require hard electronic valves and microcontrollers. Existing designs for entirely soft pneumatic control systems are capable of either digital or analog operation, but not both, and are limited by speed of actuation, range of pressure, time required for fabrication, or loss of power through pull-down resistors. Using the nonlinear mechanics intrinsic to structures composed of soft materials—in this case, by leveraging membrane inversion and tube kinking—two modular soft components are developed: a piston actuator and a bistable pneumatic switch. These two components combine to create valves capable of analog pressure regulation, simplified digital logic, controlled oscillation, nonvolatile memory storage, linear actuation, and interfacing with human users in both digital and analog formats. Three demonstrations showcase the capabilities of systems constructed from these valves: 1) a wearable glove capable of analog control of a soft artificial robotic hand based on input from a human user’s fingers, 2) a human-controlled cushion matrix designed for use in medical care, and 3) an untethered robot which travels a distance dynamically programmed at the time of operation to retrieve an object. This work illustrates pathways for complementary digital and analog control of soft robots using a unified valve design.

The rapidly increasing use of digital technologies requires the rethinking of methods to store data. This work shows that digital data can be stored in mixtures of fluorescent dye molecules, which are deposited on a surface by inkjet printing, where an amide bond tethers the dye molecules to the surface. A microscope equipped with a multichannel fluorescence detector distinguishes individual dyes in the mixture. The presence or absence of these molecules in the mixture encodes binary information (i.e., “0” or “1”). The use of mixtures of molecules, instead of sequence-defined macromolecules, minimizes the time and difficulty of synthesis and eliminates the requirement of sequencing. We have written, stored, and read a total of approximately 400 kilobits (both text and images) with greater than 99% recovery of information, written at an average rate of 128 bits/s (16 bytes/s) and read at a rate of 469 bits/s (58.6 bytes/s)., Digital data can be stored in mixtures of fluorescent dye molecules tethered to a polymeric surface. Inkjet printing of small molecules coupled with fluorescence output can store and read the data.

This paper describes measurements of charge transport by tunneling through molecular junctions comprising a self-assembled monolayer (SAM) supported by a template-stripped metal bottom electrode (M

This paper describes a surface analysis technique that uses the "EGaIn junction" to measure tunneling current densities (J(V), amps/cm2) through self-assembled monolayers (SAMs) terminated in a chelating group and incorporating different transition metal ions. Comparisons of J(V) measurements between bare chelating groups and chelates are used to characterize the composition of the SAM and infer the dissociation constant (Kd, mol/L), as well as kinetic rate constants (koff, L/mol·s; kon, 1/s) of the reversible chelate-metal reaction. To demonstrate the concept, SAMs of 11-(4-methyl-2,2'-bipyrid-4'-yl (bpy))undecanethiol (HS(CH2)11bpy) were incubated within ethanol solutions of metal salts. After rinsing and drying the surface, measurements of current as a function of incubation time and concentration in solution are used to infer koff, kon, and Kd. X-ray photoelectron spectroscopy (XPS) provides an independent measure of surface composition to confirm inferences from J(V) measurements. Our experiments establish that (i) bound metal ions are stable to the rinsing step as long as the rinsing time, τrinse ≪ 1 k o f f ; (ii) the bound metal ions increase the current density at the negative bias and reduce the rectification observed with free bpy terminal groups; (iii) the current density as a function of the concentration of metal ions in solution follows a sigmoidal curve; and (iv) the values of Kd measured using J(V) are comparable to those measured using XPS, but larger than those measured in solution. The EGaIn junction, thus, provides a new tool for the analysis of the composition of the surfaces that undergo reversible chemical reactions with species in solution.

This paper demonstrates that the molecular conformation (in addition to the composition and structure) of molecules making up self-assembled monolayers (SAMs) influences the rates of charge tunneling (CT) through them, in molecular junctions of the form AuTS/S(CH2)2CONR1R2//Ga2O3/EGaIn, where R1 and R2 are alkyl chains of different length. The lengths of chains R1 and R2 were selected to influence the conformations and conformational homogeneity of the molecules in the monolayer. The conformations of the molecules influence the thickness of the monolayer (i.e. tunneling barrier width) and their rectification ratios at ±1.0 V. When R1 = H, the molecules are well ordered and exist predominantly in trans-extended conformations. When R1 is an alkyl group (e.g., R1 ≠ H), however, their conformations can no longer be all-trans-extended, and the molecules adopt more gauche dihedral angles. This change in the type of conformation decreases the conformational order and influences the rates of tunneling. When R1 = R2, the rates of CT decrease (up to 6.3×), relative to rates of CT observed through SAMs having the same total chain lengths, or thicknesses, when R1 = H. When R1 ≠ H ≠ R2, there is a weaker correlation (relative to that when R1 = H or R1 = R2) between current density and chain length or monolayer thickness, and in some cases the rates of CT through SAMs made from molecules with different R2 groups are different, even when the thicknesses of the SAMs (as determined by XPS) are the same. These results indicate that the thickness of a monolayer composed of insulating, amide-containing alkanethiols does not solely determine the rate of CT, and rates of charge tunneling are influenced by the conformation of the molecules making up the junction.

This perspective considers ways in which the field of microfluidics can increase its impact by improving existing technologies and enabling new functionalities. We highlight applications where microfluidics has made or can make important contributions, including diagnostics, food safety, and the production of materials. The success of microfluidics assumes several forms, including fundamental innovations in fluid mechanics that enable the precise manipulation of fluids at small scales and the development of portable microfluidic chips for commercial purposes. We identify outstanding technical challenges whose resolution could increase the accessibility of microfluidics to users with both scientific and non-technical backgrounds. They include the simplification of procedures for sample preparation, the identification of materials for the production of microfluidic devices in both laboratory and commercial settings, and the replacement of auxiliary equipment with automated components for the operation of microfluidic devices.

Completely soft, autonomous fluidic robots require valves made of soft materials. Such a soft valve has been demonstrated recently to enable complex movements of soft robots using a single source of air of constant pressure. This paper studies the mechanics of the valve using a combination of experiments and calculations. The valve is made of an elastomeric tube, subject to axial compression. At critical compression, the tube snaps into a kink and blocks the flow of the air in the tube. At another critical compression, the tube snaps open the kink and lets the air flow in the tube. The instability functions as a digital, on-and-off valve, and this function is unaffected by inaccurate deformation of the ends of the tube. A kinked tube blocks fluid flow in the tube up to a certain pressure. Because the elastomer readily undergoes large and reversible deformation, the kink valve can close and open repeatedly without damage. We map out the functional characteristics of the kink valve—the kink-close compression, the kink-open compression, and the breakthrough pressure—in the design space of material and geometry. It is hoped that this study will stimulate further work to harness diverse elastic instabilities for functions needed in soft robots.

This Article describes the relationship between molecular structure, and the rectification of tunneling current, in tunneling junctions based on self-assembled monolayers (SAMs). Molecular dipoles from simple organic functional groups (amide, urea, and thiourea) were introduced into junctions with the structure AgTS/S(CH2)nR(CH2)mCH3//Ga2O3/EGaIn. Here, R is an n-alkyl fragment (−CH2−)2 or 3, an amide group (either −CONH– or −NHCO−), a urea group (−NHCONH−), or a thiourea group (−NHCSNH−). The amide, urea, or thiourea groups introduce a localized electric dipole moment into the SAM and change the polarizability of that section of the SAM, but do not produce large, electronically delocalized groups or change other aspects of the tunneling barrier. This local change in electronic properties correlates with a statistically significant, but not large, rectification of current (r+) at ±1.0 V (up to r+ ≈ 20). The results of this work demonstrate that the simplest form of rectification of current at ±1.0 V, in E...

The nature of the processes at the origin of life that selected specific classes of molecules for broad incorporation into cells is controversial. Among those classes selected were polyisoprenoids and their derivatives. This paper tests the hypothesis that polyisoprenoids were early contributors to membranes in part because they (or their derivatives) could facilitate charge transport by quantum tunneling. It measures charge transport across self-assembled monolayers (SAMs) of carboxyl-terminated monoterpenoids (O2 C(C9 HX)) and alkanoates (O2 C(C7 HX)) with different degrees of unsaturation, supported on silver (AgTS ) bottom electrodes, with Ga2 O3 /EGaIn top electrodes. Measurements of current density of SAMs of linear length-matched hydrocarbons-both saturated and unsaturated-show that completely unsaturated molecules transport charge faster than those that are completely saturated by approximately a factor of ten. This increase in relative rates of charge transport correlates with the number of carbon-carbon double bonds, but not with the extent of conjugation. These results suggest that polyisoprenoids-even fully unsaturated-are not sufficiently good tunneling conductors for their conductivity to have favored them as building blocks in the prebiotic world.

[Image: see text] Although information is ubiquitous, and its technology arguably among the highest that humankind has produced, its very ubiquity has posed new types of problems. Three that involve storage of information (rather than computation) include its usage of energy, the robustness of stored information over long times, and its ability to resist corruption through tampering. The difficulty in solving these problems using present methods has stimulated interest in the possibilities available through fundamentally different strategies, including storage of information in molecules. Here we show that storage of information in mixtures of readily available, stable, low-molecular-weight molecules offers new approaches to this problem. This procedure uses a common, small set of molecules (here, 32 oligopeptides) to write binary information. It minimizes the time and difficulty of synthesis of new molecules. It also circumvents the challenges of encoding and reading messages in linear macromolecules. We have encoded, written, stored, and read a total of approximately 400 kilobits (both text and images), coded as mixtures of molecules, with greater than 99% recovery of information, written at an average rate of 8 bits/s, and read at a rate of 20 bits/s. This demonstration indicates that organic and analytical chemistry offer many new strategies and capabilities to problems in long-term, zero-energy, robust information storage.

Although soft devices (grippers, actuators, and elementary robots) are rapidly becoming an integral part of the broad field of robotics, autonomy for completely soft devices has only begun to be developed. Adaptation of conventional systems of control to soft devices requires hard valves and electronic controls. This paper describes completely soft pneumatic digital logic gates having a physical scale appropriate for use with current (macroscopic) soft actuators. Each digital logic gate utilizes a single bistable valve-the pneumatic equivalent of a Schmitt trigger-which relies on the snap-through instability of a hemispherical membrane to kink internal tubes and operates with binary high/low input and output pressures. Soft, pneumatic NOT, AND, and OR digital logic gates-which generate known pneumatic outputs as a function of one, or multiple, pneumatic inputs-allow fabrication of digital logic circuits for a set-reset latch, two-bit shift register, leading-edge detector, digital-to-analog converter (DAC), and toggle switch. The DAC and toggle switch, in turn, can control and power a soft actuator (demonstrated using a pneu-net gripper). These macroscale soft digital logic gates are scalable to high volumes of airflow, do not consume power at steady state, and can be reconfigured to achieve multiple functionalities from a single design (including configurations that receive inputs from the environment and from human users). This work represents a step toward a strategy to develop autonomous control-one not involving an electronic interface or hard components-for soft devices.

How simple chemical reactions self-assembled into complex, robust networks at the origin of life is unknown. This general problem-self-assembly of dissipative molecular networks-is also important in understanding the growth of complexity from simplicity in molecular and biomolecular systems. Here, we describe how heterogeneity in the composition of a small network of oscillatory organic reactions can sustain (rather than stop) these oscillations, when homogeneity in their composition does not. Specifically, multiple reactants in an amide-forming network sustain oscillation when the environment (here, the space velocity) changes, while homogeneous networks-those with fewer reactants-do not. Remarkably, a mixture of two reactants of different structure-neither of which produces oscillations individually-oscillates when combined. These results demonstrate that molecular heterogeneity present in mixtures of reactants can promote rather than suppress complex behaviors.

This paper describes the use of surface plasmon resonance spectroscopy and self-assembled monolayers (SAMs) of alkanethiols on gold to evaluate the ability of surfaces terminating in different combinations of charged groups to resist the nonspecific adsorption of proteins from aqueous buffer. Mixed SAMs formed from a 1:1 combination of a thiol terminated in a trimethylammonium group and a thiol terminated in a sulfonate group adsorbed less than 1% of a monolayer of two proteins with different characteristics: fibrinogen and lysozyme. Single-component SAMs formed from thiols terminating in groups combining a positively charged moiety and a negatively charged moiety were also capable of resisting the adsorption of proteins. Single-component SAMs presenting single charges adsorbed nearly a full monolayer of protein. The amount of protein that adsorbed to mixed zwitterionic SAMs did not depend on the ionic strength or the pH of the buffer in which the protein was dissolved. The amount of protein that adsorbed to single-component zwitterionic SAMs increased as the ionic strength of the buffer decreased; it also decreased as the pH of the buffer increased (at constant ionic strength). Single-component zwitterionic SAMs composed of thiols terminating in

Locomotion of an organism interacting with an environment is the consequence of a symmetry-breaking action in space-time. Here we show a minimal instantiation of this principle using a thin circular sheet, actuated symmetrically by a pneumatic source, using pressure to change shape nonlinearly via a spontaneous buckling instability. This leads to a polarized, bilaterally symmetric cone that can walk on land and swim in water. In either mode of locomotion, the emergence of shape asymmetry in the sheet leads to an asymmetric interaction with the environment that generates movement--via anisotropic friction on land, and via directed inertial forces in water. Scaling laws for the speed of the sheet of the actuator as a function of its size, shape, and the frequency of actuation are consistent with our observations. The presence of easily controllable reversible modes of buckling deformation further allows for a change in the direction of locomotion in open arenas and the ability to squeeze through confined environments--both of which we demonstrate using simple experiments. Our simple approach of harnessing elastic instabilities in soft structures to drive locomotion enables the design of novel shape-changing robots and other bioinspired machines at multiple scales.

This paper addresses the mechanism for rectification in molecular tunneling junctions based on alkanethiolates terminated by a bipyridine group complexed with a metal ion, that is, having the structure Au

This work demonstrates that a soft, toroidal hydrostat can be used to perform three functions found in both living and engineered systems: gripping, catching, and conveying. We first demonstrate a gripping mechanism that uses linear motion to drive the inversion of the toroid around objects, encapsulating them within a crumpled elastic membrane under hydrostatic pressure. This mechanism results in gripping forces ranging from 1–80 N, which depend predictably upon the geometric and material properties of the gripper and the object. We next demonstrate a catching mechanism akin to that of a chameleon’s tongue: the elasticity of the membrane is used to store mechanical energy and drive a rapid acceleration and inversion process (≈400 m/s2) to capture flying objects (e.g., a bouncing ball). Finally, we show how the soft topological structure can be implemented in a soft conveying mechanism which continuously inverts and passes objects through its center (~1 cm/s), serving a function like that of esophageal peristalsis (i.e., transporting objects through a tube), while eliminating the requirement of a lubricated interface and the coordinated actuation of a pressure wave. The hybrid hard-soft mechanisms presented here can be applied in the integration of soft functionality into conventional robotic systems for applications including the automation of agricultural and biological research processes. More generally, we show how inflatable structures comprising soft polymeric films arranged in complex topologies provide a promising approach to designing soft robotic systems with novel, bio-inspired functionality.

Soft robots have attracted attention for biomedical and consumer devices. However, most of these robots are pneumatically actuated, requiring a tether and thus limiting wearable applications that require multiple controlled actuators. By pairing liquid-vapor phase change actuation with a textile-based laminated manufacturing method, smart thermally actuating textiles (STATs) eliminate the need for a pneumatic tether. STATs are lightweight and unobtrusive for wearable applications and exploit a facile manufacturing approach that supports arbitrary customization of the form factor and easy creation of connected arrays of individual robotic modules. Through integrated sensing and heating elements, STATs demonstrate closed-loop feedback that enables dynamic pressure control in the presence of environmental temperature fluctuations.