Paul J. Wesson

Writing Self‐Erasing Images using Metastable Nanoparticle “Inks”

Fans of the “Mission Impossible” movies might recall the selfdestructing messages used to brief the secret agent on the details of his new mission. Even beyond the realm of fictitious espionage, materials that store textual or graphical information for a prescribed period of time are desirable for applications in secure communications. 2] Furthermore, if such materials are rewritable, they can help to limit the use of traditional paper, thereby reducing the costs, both industrial and environmental, associated with paper production and recycling. To date, most research on self-erasing media has relied on the use of photochromic molecules—that is, molecules that isomerize and change color when exposed to light of appropriate wavelength—embedded in or attached to a polymeric or gel matrix. In one widely publicized example, Xerox Corporation recently announced the development of photochromic paper that self-erases in 16 to 24 h. While writing with light can be both rapid and accurate, 7] photochromic “inks” are not necessarily optimal for transforming light-intensity patterns into color variations, because they have relatively low extinction coefficients, are prone to photobleaching, and usually offer only two colors corresponding to the two states of photoisomerizing molecules. Herein, we describe a conceptually different self-erasing material in which both the “writing” and self-erasure of color images are controlled by the dynamic non-equilibrium aggregation of photoresponsive metal (here, gold and silver) nanoparticles (Au and AgNPs “inks”) embedded in thin, flexible organogel films. When exposed to UV light, the trans-azobenzene groups coating the NPs isomerize to cisazobenzene with a large dipole moment. As a result, the NPs aggregate into supraspherical (SS) assemblies, whose apparent color depends on the duration of UV irradiation (Figures 1 and 2). Since the SS are metastable and fall apart spontaneously in the absence of UV irradiation, the two-color and multicolor images written into the films gradually self-erase (Figures 2 and 3). The erasure times can be controlled by the number of dipoles induced on the nanoparticles and can also be accelerated by exposure to visible light or by heating the material. Multiple images can be written into the same film either concurrently or after erasure.

Maze solving by chemotactic droplets

Droplets emitting surface-active chemicals exhibit chemotaxis toward low-pH regions. Such droplets are self-propelled and navigate through a complex maze to seek a source of acid placed at one of the mazes exits. In doing so, the droplets find the shortest path through the maze. Chemotaxis and maze solving are due to an interplay between acid/base chemistry and surface tension effects.

Metal Nanoparticles Functionalized with Molecular and Supramolecular Switches

Weakly protected metal nanoparticles (MNPs) are used as precursors for the preparation of catenane- and pseudorotaxane-decorated NPs of various compositions (gold, palladium, platinum). When attached to the surface of MNPs, the molecular switches retain their switching abilities. The redox potentials of these switches depend on and can be regulated by the composition of the mixed self-assembled monolayers covering the MNPs.

Contact Electrification between Identical Materials

Pieces of identical, atomically flat insulators separate a charge Q when brought into contact and then parted. Repeated contacts cause the magnitudes of the separated charges to increase monotonically. A theoretical model is presented that explains these phenomena by the inherent, molecular-scale fluctuations in the composition of the seemingly identical contacting surfaces.

Coordinative self-assembly and solution-phase X-ray structural characterization of cavity-tailored porphyrin boxes

Combining linear Zn porphyrin trimers with orthogonally derivatized porphyrin dimers leads rapidly and spontaneously to the formation of monodisperse, torsionally constrained boxes comprising six components and a total of 16 metalloporphyrins. In situ X-ray scattering measurements confirm the formation of monodisperse assemblies of precisely the size expected from model box structures. While simple subunits yield highly symmetrical boxes, we find that sterically demanding subunits produce unusual twisted boxes. Previous studies of porphyrin-based box-like assemblies (squares) for selective catalysis and molecular sieving revealed two function-inhibiting structural problems: torsional motion along the metal-porphyrin-metal axis and ambiguous outside versus inside functionalization (via axial ligation of available Zn(II) sites). The new 16-porphyrin box assemblies eliminate both problems.

A bistable poly[2]catenane forms nanosuperstructures

Side-chain poly[2]catenanes at the click of a switch! A bistable side-chain poly[2]catenane has been synthesized and found to form hierarchical self-assembled hollow superstructures of nanoscale dimensions in solution. Molecular electromechanical switching (see picture) of the material is demonstrated, and the ground-state equilibrium thermodynamics and switching kinetics are examined as the initial steps towards processible molecular-based electronic devices and nanoelectromechanical systems.

Molecular-Mechanical Switching at the Nanoparticle-Solvent Interface: Practice and Theory

A range (Au, Pt, Pd) of metal nanoparticles (MNPs) has been prepared and functionalized with (a) redox-active stalks containing tetrathiafulvalene (TTF) units, (b) [2]pseudorotaxanes formed between these stalks and cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings, and (c) bistable [2]rotaxane molecules where the dumbbell component contains a 1,5-dioxynaphthalene (DNP) unit, as well as a TTF unit, encircled by a CBPQT(4+) ring. It transpires that the molecules present in (a) and (c) and the supermolecules described in (b) retain their switching characteristics, previously observed in solution, when they are immobilized onto MNPs. Moreover, their oxidation potentials depend on the fraction, chi, of the molecules or supermolecules on the surface of the nanoparticles. A variation in chi affects the oxidation potentials of the TTF units to the extent that switching can be subjected to fine tuning as a result. Specifically, increasing chi results in positive shifts (i) in the oxidation potentials of the TTF unit in (a)-(c) and (ii) the reduction potentials of the CBPQT(4+) rings in (c). These shifts can be attributed to an increase in the electrostatic potential surrounding the MNPs. Both the magnitude and the direction of these shifts are reproduced by a model, based on the Poisson-Boltzmann equation coupled with charge-regulating boundary conditions. Furthermore, the kinetics of relaxation from the metastable state coconformation (MSCC) to the ground-state coconformation (GSCC) of the bistable [2]rotaxane molecules also depends on chi, as well as on the nanoparticle diameter. Increasing either of these parameters accelerates the rate of relaxation from the MSCC to the GSCC. This rate is a function of (i) the activation energy for the relaxation process associated with the bistable [2]rotaxane molecules in solution and (ii) the electrostatic potential surrounding the MNPs. The electrostatic potential depends on (i) the diameter of the MNPs, (ii) the amount of the bistable [2]rotaxane molecules on the surface of the MNPs, and (iii) the equilibrium distribution of the CBPQT(4+) rings between the DNP and TTF recognition sites in the GSCC. This electrostatic potential has also been quantified using the Poisson-Boltzmann equation, leading to faithful estimates of the rate constants.

Dynamic internal gradients control and direct electric currents within nanostructured materials

Switchable nanomaterials--materials that can change their properties and/or function in response to external stimuli-have potential applications in electronics, sensing and catalysis. Previous efforts to develop such materials have predominately used molecular switches that can modulate their properties by means of conformational changes. Here, we show that electrical conductance through films of gold nanoparticles coated with a monolayer of charged ligands can be controlled by dynamic, long-range gradients of both mobile counterions surrounding the nanoparticles and conduction electrons on the nanoparticle cores. The internal gradients and the electric fields they create are easily reconfigurable, and can be set up in such a way that electric currents through the nanoparticles can be modulated, blocked or even deflected so that they only pass through select regions of the material. The nanoion/counterion hybrids combine the properties of electronic conductors with those of ionic gels/polymers, are easy to process by solution-casting and, by controlling the internal gradients, can be reconfigured into different electronic elements (current rectifiers, switches and diodes).

Gene Therapy Vectors with Enhanced Transfection Based on Hydrogels Modified with Affinity Peptides

Regenerative strategies for damaged tissue aim to present biochemical cues that recruit and direct progenitor cell migration and differentiation. Hydrogels capable of localized gene delivery are being developed to provide a support for tissue growth, and as a versatile method to induce the expression of inductive proteins; however, the duration, level, and localization of expression is often insufficient for regeneration. We thus investigated the modification of hydrogels with affinity peptides to enhance vector retention and increase transfection within the matrix. PEG hydrogels were modified with lysine-based repeats (K4, K8), which retained approximately 25% more vector than control peptides. Transfection increased 5- to 15-fold with K8 and K4 respectively, over the RDG control peptide. K8- and K4-modified hydrogels bound similar quantities of vector, yet the vector dissociation rate was reduced for K8, suggesting excessive binding that limited transfection. These hydrogels were subsequently applied to an in vitro co-culture model to induce NGF expression and promote neurite outgrowth. K4-modified hydrogels promoted maximal neurite outgrowth, likely due to retention of both the vector and the NGF. Thus, hydrogels modified with affinity peptides enhanced vector retention and increased gene delivery, and these hydrogels may provide a versatile scaffold for numerous regenerative medicine applications.

Measurement of protein-ligand binding constants from reaction-diffusion concentration profiles.

Protein-ligand dissociation constants, K(d), are determined precisely and down to the picomolar range from reaction-diffusion (RD) concentration profiles created by proteins diffusing through hydrogels functionalized with protein ligands. The RD process effectively amplifies the molecular-scale binding events into macroscopic patterns visible to the naked eye. The method is applicable to various protein-ligand pairs and does not require any prior knowledge about the protein structure.