Tuning Optical Properties of Plasmonic Aerosols through Ligand-Solvent Interactions.

Plasmonic nanoparticles are highly tunable light-harvesting materials with a wide array of applications in photonics and catalysis. More recently, there has been interest in using aerosolized plasmonic nanoparticles for cloud formation, airborne photocatalysts, and molecular sensors, all of which take advantage of the large scattering cross sections and the ability of these particles to support intense local field enhancement ("hot spots"). While extensive research has investigated properties of plasmonic particles in the solution phase, surfaces, and films, aerosolized plasmonics are relatively unexplored. Here, we demonstrate how the capping ligand, suspension solvent, and atomization conditions used for aerosol generation control the steady-state optical properties of aerosolized Silica@Au plasmonic nanoshells. Our experimental results, supported with spectral simulations, illustrate that ligand coverage and atomization conditions control the degree of solvent retention and thus the spectral characteristics and potential access to surfaces for catalysis in the aerosol phase, opening a new regime for tunable applications of plasmonic metamaterials.

Cell-Free Protein Expression in Polymer Materials.

While synthetic biology has advanced complex capabilities such as sensing and molecular synthesis in aqueous solutions, important applications may also be pursued for biological systems in solid materials. Harsh processing conditions used to produce many synthetic materials such as plastics make the incorporation of biological functionality challenging. One technology that shows promise in circumventing these issues is cell-free protein synthesis (CFPS), where core cellular functionality is reconstituted outside the cell. CFPS enables genetic functions to be implemented without the complications of membrane transport or concerns over the cellular viability or release of genetically modified organisms. Here, we demonstrate that dried CFPS reactions have remarkable tolerance to heat and organic solvent exposure during the casting processes for polymer materials. We demonstrate the utility of this observation by creating plastics that have spatially patterned genetic functionality, produce antimicrobials in situ, and perform sensing reactions. The resulting materials unlock the potential to deliver DNA-programmable biofunctionality in a ubiquitous class of synthetic materials.

The low-lying electronic states and ultrafast relaxation dynamics of the monomers and J-aggregates of meso-tetrakis (4-sulfonatophenyl)-porphyrins.

The electronic and vibrational spectra of the meso-tetrakis(4-sulfonatophenyl)-porphyrins (TSPP) have been studied computationally using the PFD-3B functional with time-dependent density functional theory for the excited states. The calculated UV-vis absorption and emission spectra in aqueous solution are in excellent agreement with the experimental measurements of both H2TSPP-4 (monomer) at high pH and H4TSPP-2 (forming J-aggregate) at low pH. Moreover, our calculations reveal an infrared absorption at 1900 cm-1 in the singlet and triplet excited states that is absent in the ground state, which is chosen as a probe for transient IR absorption spectroscopy to investigate the vibrational dynamics of the excited state. Specifically, the S2 to S1 excited state internal conversion process time, the S1 state vibrational relaxation time, and the lifetime of the S1 excited electronic state are all quantitatively deduced.

Quantitative Modeling of Electron Dynamics and the Effect of Diffusion in Photosensitized Semiconductor Nanocomposites.

Photosensitized semiconducting nanomaterials have received considerable attention because of their applications in photocatalytic and photoelectronic devices. In such systems, photoexcited electrons with sufficiently high energies can be injected into the conduction band (CB) of an adjacent semiconductor. These excited electrons are subjected to various physical processes that can lead to their annihilation before exercising their catalytic/electric functions, and the efficiency of the photosensitized functions depends on the quantity of CB electrons produced and how long they remain near the surface region of the semiconductor. The rise and decay of photoexcited electrons in the semiconductor CB can be probed with transient IR absorption (TA), which was first demonstrated by Lian and co-workers. Results from various laboratories have since revealed that electrons appear in the CB following the excitation of the photosensitizer in tens to hundreds of femtoseconds and that the decay of the CB electrons typically exhibits multiple exponentials on varying ultrafast time scales. The size of the semiconductor nanoparticle appears to influence the diffusion of the CB electrons and thus their lifetimes. In all studies reported, the observed multiexponential decays have been analyzed and interpreted using purely phenomenological models, in which the individual decays were intuitively assigned to one specific relaxation or loss process. In reality, however, each exponential decay can be a convolution of multiple physical processes. In this Account, we report a universally applicable physical model, constructed by including all known electron dynamic processes, to quantitatively account for the multiexponential decays. We characterize the model as universal, as it can be used to analyze our own TA measurements, as well as data acquired in other laboratories. In our study of TiO2 nanorods photosensitized by Ag platelets, we demonstrate that each of the observed triple-exponential decays corresponds to a convolution of several physical decay processes occurring on similar time scales. The rate of each of the processes can be deconvoluted and determined to construct a complete, physically based model to assess the most important question: How many CB electrons are near the semiconductor surface region and what is their lifetime?The size of the semiconductor is an important consideration. Intuitively, as the semiconductor volume increases, there is more room for CB electrons to diffuse around, which increases their lifetime as annihilation occurs primarily at the surface. Indeed, Tachiya and co-workers previously reported that this lifetime increases with particle size. Nevertheless, while CB electrons live longer in the bulk of the particle, they are only useful when they are at the surface. Overall, what really matters is the CB electrons near the surface region, where the photosensitized functions actually occur. In applying our model to analyze the previously reported size-dependent Au/TiO2 results, we successfully reproduced the observation that larger semiconductor nanoparticles lengthen the lifetime of CB electrons because of diffusion into the bulk. More importantly, however, our model reveals that the size of the semiconductor has almost no influence on the retention of CB electrons near the semiconductor surface. This information is only revealed when all physical processes are quantitatively taken into account for the observed electron dynamics, which is not feasible with a phenomenological approach.

Ag nanoplatelets as efficient photosensitizers for TiO2 nanorods.

The lifetime for injecting hot electrons generated in Ag nanoplatelets to nearby TiO2 nanorods was measured with ultrafast transient IR absorption to be 13.1 ± 1.5 fs, which is comparable to values previously reported for much smaller spherical Ag nanoparticles. Although it was shown that the injection rate decreases as the particle size increases, this observation can be explained by the facts that (1) the platelet has a much larger surface to bulk ratio and (2) the platelet affords a much larger surface area for direct contact with the semiconductor. These two factors facilitate strong Ag-TiO2 coupling (as indicated by the observed broadened surface plasmon resonance band of Ag) and can explain why Ag nanoplatelets have been found to be more efficient than much smaller Ag nanoparticles as photosensitizers for photocatalytic functions. The fast injection rate, together with a stronger optical absorption in comparison with Au and dye molecules, make Ag nanoplatelets a preferred photosensitizer for wide bandgap semiconductors.

Effects of Molecular Structure and Solvent Polarity on Adsorption of Carboxylic Anchoring Dyes onto TiO2 Particles in Aprotic Solvents.

Interactions of molecules with the surface of TiO2 particles are of fundamental and technological importance. One example is that the adsorption density and energy of the dye molecules on TiO2 particles affect the efficiency of dye-sensitized solar cells (DSSC). In this work, we present measurements characterizing the adsorption of the two isomers, para-ethyl red (p-ER) and ortho-ethyl red (o-ER), of a dye molecule potentially applicable for DSSC onto TiO2 particles by second harmonic scattering (SHS). It is found that while at the wavelengths used here o-ER has a much bigger molecular hyperpolarizability, p-ER exhibits strong SHS responses but o-ER gives no detectable SHS when the dyes are added to the TiO2 colloids, respectively. This observation indicates that o-ER does not adsorb onto TiO2, likely due to steric hindrance. Furthermore, we investigate how solvents affect the surface adsorption strength and density of p-ER onto TiO2 in four aprotic solvents with varying polarity. The absolute magnitude of the adsorption free energy was found to increase with the specific solvation energy that represents the ability of accepting electrons and solvent polarity. It is likely that resolvation of the solvent molecules displaced by the adsorption of the dye molecule at the surface in stronger electron-accepting and more polar solvents results in a larger adsorption free energy for the dye adsorption.