Michael J. Tauber

Rapid self-healing hydrogels

Synthetic materials that are capable of autonomous healing upon damage are being developed at a rapid pace because of their many potential applications. Despite these advancements, achieving self-healing in permanently cross-linked hydrogels has remained elusive because of the presence of water and irreversible cross-links. Here, we demonstrate that permanently cross-linked hydrogels can be engineered to exhibit self-healing in an aqueous environment. We achieve this feature by arming the hydrogel network with flexible-pendant side chains carrying an optimal balance of hydrophilic and hydrophobic moieties that allows the side chains to mediate hydrogen bonds across the hydrogel interfaces with minimal steric hindrance and hydrophobic collapse. The self-healing reported here is rapid, occurring within seconds of the insertion of a crack into the hydrogel or juxtaposition of two separate hydrogel pieces. The healing is reversible and can be switched on and off via changes in pH, allowing external control over the healing process. Moreover, the hydrogels can sustain multiple cycles of healing and separation without compromising their mechanical properties and healing kinetics. Beyond revealing how secondary interactions could be harnessed to introduce new functions to chemically cross-linked polymeric systems, we also demonstrate various potential applications of such easy-to-synthesize, smart, self-healing hydrogels.

Infrared Nanoscopy of Dirac Plasmons at the Graphene-SiO₂ Interface

We report on infrared (IR) nanoscopy of 2D plasmon excitations of Dirac fermions in graphene. This is achieved by confining mid-IR radiation at the apex of a nanoscale tip: an approach yielding 2 orders of magnitude increase in the value of in-plane component of incident wavevector q compared to free space propagation. At these high wavevectors, the Dirac plasmon is found to dramatically enhance the near-field interaction with mid-IR surface phonons of SiO(2) substrate. Our data augmented by detailed modeling establish graphene as a new medium supporting plasmonic effects that can be controlled by gate voltage.

Flowing liquid sample jet for resonance Raman and ultrafast optical spectroscopy

A wire-guided, gravity-driven jet apparatus is described that produces optically stable thin films of liquids flowing at rates suitable for high repetition rate spectroscopy. Unlike conventional free-flowing jets, the design works well for low viscosity solvents including water and aqueous solutions of proteins. The construction of the wire guide, jet nozzle, and flow system is described. A stable water film whose thickness can be varied from 6 to 100 μm is demonstrated that has been employed in resonance Raman and femtosecond transient absorption experiments.

Toward an n-type molecular wire: electron hopping within linearly linked perylenediimide oligomers.

A series of linearly linked perylenediimide (PDI) dimers and trimers were synthesized in which the PDI pi systems are nearly orthogonal. These oligomers and several model compounds were singly reduced, and intramolecular electron hopping between the PDI molecules was probed by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy. When the functional groups attached to the ends of the oligomers were chosen to make each PDI molecule electronically equivalent, the single electron hops between the PDI molecules with rates that significantly exceed 10(7) s(-1). Rapid electron hopping between pairs of PDI molecules having orthogonal pi systems is unexpected and may expand the possible design motifs for organic electronic materials based on PDI.

Dye-Sensitized Solar Cell Constructed with Titanium Mesh and 3-D Array of TiO2 Nanotubes†

We have designed and constructed dye sensitized solar cells based on new, 3-D configurations of TiO(2) nanotubes. The overall efficiency of our best cells is 5.0% under standard air mass 1.5 global (AM 1.5 G) solar conditions, and the incident photon-to-current efficiency exceeds 60% over a broad part of the visible spectrum. Unlike prior nanotube-based cells where tubes are grown vertically in a 2-D array, the anodes of the present cells consist of tubes that extend radially in a 3-D array from a grid of fine titanium wires. The nanotubes are tens of micrometers in length, and the radial nature of the anode allows the photon absorption path length to exceed the electron transport distance (nanotube length). The cells are front-illuminated and do not require a transparent conductive oxide substrate at either the anode or cathode. The use of 3-D configured nanotubes and low-resistance titanium metal substrates are expected to enhance the performance and simplify the construction of large area dye-sensitized solar cells.

Analysis of the Mode-Specific Excited-State Energy Distribution and Wavelength-Dependent Photoreaction Quantum Yield in Rhodopsin

The photoreaction quantum yield of rhodopsin is wavelength dependent: phi(lambda) is reduced by up to 5% at wavelengths to the red of 500 nm but is invariant (phi = 0.65 +/- 0.01) between 450 and 500 nm (Kim et al., 2001). To understand this nonstatistical internal conversion process, these results are compared with predictions of a Landau-Zener model for dynamic curve crossing. The initial distribution of excess photon energy in the 28 Franck-Condon active vibrational modes of rhodopsin is defined by a fully thermalized sum-over-states vibronic calculation. This calculation reveals that absorption by high-frequency unreactive modes (e.g., C[double bond]C stretches) increases as the excitation wavelength is shifted from 570 to 450 nm whereas relatively less energy is deposited into reactive low-frequency modes. This result qualitatively explains the experimentally observed wavelength dependence of phi(lambda) for rhodopsin and reveals the importance of delocalized, torsional modes in the reactive pathway.

Characterization of carotenoid aggregates by steady-state optical spectroscopy.

The carotenoids have low-lying triplet excited states and can self-assemble in some solvents to form weakly or strongly coupled aggregates. These qualities make carotenoid aggregates useful for studies of singlet fission, where an outstanding goal is the correlation of interchromophoric coupling to the dynamics and yield of triplet excited states from a parent singlet excited state. Three aggregates of zeaxanthin, two weakly coupled and one strongly coupled, are characterized by steady-state spectroscopic methods including temperature-dependent absorption, fluorescence, and resonance Raman spectroscopy. The absorption spectra for each type of aggregate are distinct; however, an analysis of band positions reveals some important shared characteristics and suggests that the strongly coupled H-aggregate contains a subpopulation of weakly coupled constituents. Temperature-dependent absorption spectroscopy indicates that one of the weakly coupled aggregates can be converted to the other upon heating. The emission spectra of the three aggregates have similar profiles that are overall red-shifted by more than 1000 cm(-1) relative to the monomer. The emission quantum yields of the aggregates are 5 to 30 times less than that of the monomer, with the lowest yield for the strongly coupled aggregate. The vibrational spectra of the chromophores support only slight perturbations from the structure of solvated monomers. Our findings support the conclusion that all three aggregates are best characterized as H-aggregates, in agreement with a prior theoretical study of lutein aggregates.

Raman microspectroscopy and vibrational sum frequency generation spectroscopy as probes of the bulk and surface compositions of size-resolved sea spray aerosol particles

Sea spray aerosol (SSA) represents one of the largest aerosol components in our atmosphere. SSA plays a major role in influencing climate; however the overall impacts remain poorly understood due to the overall chemical complexity. SSA is comprised of a mixture of inorganic and organic components in varying proportions that change as a function of particle size and seawater composition. In this study, nascent SSA particles were produced using breaking waves, resulting in compositions and sizes representative of the open ocean. The composition of individual SSA particles ranging in size from ca. 0.15 to 10 μm is measured using Raman microspectroscopy, while the interfacial composition of collections of size-resolved particles is probed by sum frequency generation (SFG). Raman spectra of single particles have bands in the 980 to 1030 cm(-1) region associated with the symmetric stretch of the sulfate anion, the 2800 to 3000 cm(-1) region associated with carbon-hydrogen stretches, and from 3200-3700 cm(-1) associated with the oxygen-hydrogen stretches of water. The relative intensities of these features showed a strong dependence on particle size. In particular, submicrometer particles exhibited a larger amount of organic matter compared to supermicrometer particles. However, for external surfaces of homogeneous SSA particles (i.e. particles without a solid inclusion), and also the interfaces of mixed-phase particles, there was a strong SFG response in the aliphatic C-H stretching region for both sub- and supermicrometer particles. This finding suggests that organic material present in supermicrometer particles primarily resides at the interface. The presence of methylene contributions in the SFG spectra indicated disordered alkyl chains, in contrast to what one might expect for a surfactant layer on a sea salt particle. Changes in peak frequencies and relative intensities in the C-H stretching region are seen for some particles after the addition of bacteria, phytoplankton, and growth medium to the seawater. This study provides new insights into the bulk and surface composition of SSA particles and represents a step forward in our understanding of this globally abundant aerosol. It also provides insights into the development of model systems for SSA that may more accurately represent the organic layer at the surface.

Resonance Raman spectra and vibronic analysis of the aqueous solvated electron

Abstract Resonance Raman spectra of the aqueous solvated electron reveal enhancements of the water inter- and intramolecular vibrations demonstrating that electronic excitation is significantly coupled to these modes. The Raman cross-sections and absorption spectra are quantitatively modeled, yielding an optimized Gaussian homogeneous broadening of 4660 cm −1 (FWHM), inhomogeneous broadening of 2700 cm −1 , and Franck–Condon displacements (Δ) of ∼1 for each of the three librations, 0.4 for the water bend, and 0.2 for the stretch. Frequency downshifts of the resonantly enhanced H2O bend to 1615 cm −1 , and of the stretch to 3100 cm −1 are best explained by charge donation into solvent frontier orbitals.

Triplet Excitons of Carotenoids Formed by Singlet Fission in a Membrane

Despite these find-ings, basic aspects of fission in LHCs, notably the identity ofthe participating chromophores, remain unclear. Intermolecularsinglet fission between two carotenoids, or between a carote-noid and bacteriochlorophyll molecule, have both been pro-posed in the LHCs of Rhodospirillum rubrum and Rhodobactersphaeroides.