Quantitative analysis of gas phase molecular constituents using frequency-modulated rotational spectroscopy.

Rotational spectroscopy has been used for decades for virtually unambiguous identification of gas phase molecular species, but it has rarely been used for the quantitative analysis of molecular concentrations. Challenges have included the nontrivial reconstruction of integrated line strengths from modulated spectra, the correlation of pressure-dependent line shape and strength with partial pressure, and the multiple standing wave interferences and modulation-induced line shape asymmetries that sensitively depend on source-chamber-detector alignment. Here, we introduce a quantitative analysis methodology that overcomes these challenges, reproducibly and accurately recovering gas molecule concentrations using a calibration procedure with a reference gas and a conversion based on calculated line strengths. The technique uses frequency-modulated rotational spectroscopy and recovers the integrated line strength from a Voigt line shape that spans the Doppler- and pressure-broadened regimes. Gas concentrations were accurately quantified to within the experimental error over more than three orders of magnitude, as confirmed by the cross calibration between CO and N2O and by the accurate recovery of the natural abundances of four N2O isotopologues. With this methodology, concentrations of hundreds of molecular species may be quantitatively measured down to the femtomolar regime using only a single calibration curve and the readily available libraries of calculated integrated line strengths, demonstrating the power of this technique for the quantitative gas-phase detection, identification, and quantification.

Polymer-Directed Growth of Plasmonic Aluminum Nanocrystals.

The challenge of controllable chemical synthesis of aluminum nanocrystals (Al NCs) has been met with only limited success. A major barrier is the absence of effective ligands to control the nucleation and growth of Al NCs. Here we demonstrate the size- and shape-controlled synthesis of monodisperse Al NCs using a polymer ligand, cumyl dithiobenzoate-terminated polystyrene (CDTB-PS). Density functional theory (DFT) calculations indicate that CDTB-PS shows selective absorption on Al{100} facets, inducing the formation of nanocubes and trigonal bipyramids. An excess of CDTB-PS, however, decreases the supersaturation of Al atoms, leading to the formation of {111} facet-terminated octahedral and triangular plates. The concentration of the catalyst, titanium (IV) isopropoxide, determines the size of Al NCs by controlling the number of seeds. Depending on nanoparticle size, the solutions of Al NCs possess distinct colors, a characteristic feature of plasmonic nanomaterials. This robust and controlled chemical synthesis of Al NCs lays a foundation for Al as a sustainable plasmonic material for current and future applications.

Understanding Resonant Light-Triggered DNA Release from Plasmonic Nanoparticles.

Nanoparticle-based platforms for gene therapy and drug delivery are gaining popularity for cancer treatment. To improve therapeutic selectivity, one important strategy is to remotely trigger the release of a therapeutic cargo from a specially designed gene- or drug-laden near-infrared (NIR) absorbing gold nanoparticle complex with NIR light. While there have been multiple demonstrations of NIR nanoparticle-based release platforms, our understanding of how light-triggered release works in such complexes is still limited. Here, we investigate the specific mechanisms of DNA release from plasmonic nanoparticle complexes using continuous wave (CW) and femtosecond pulsed lasers. We find that the characteristics of nanoparticle-based DNA release vary profoundly from the same nanoparticle complex, depending on the type of laser excitation. CW laser illumination drives the photothermal release of dehybridized single-stranded DNA, while pulsed-laser excitation results in double-stranded DNA release by cleavage of the Au-S bond, with negligible local heating. This dramatic difference in DNA release from the same DNA-nanoparticle complex has very important implications in the development of NIR-triggered gene or drug delivery nanocomplexes.

Charge Transfer Plasmons: Optical Frequency Conductances and Tunable Infrared Resonances.

A charge transfer plasmon (CTP) appears when an optical-frequency conductive pathway between two metallic nanoparticles is established, enabling the transfer of charge between nanoparticles when the plasmon is excited. Here we investigate the properties of the CTP in a nanowire-bridged dimer geometry. Varying the junction geometry controls its conductance, which modifies the resonance energies and scattering intensities of the CTP while also altering the other plasmon modes of the nanostructure. Reducing the junction conductance shifts this resonance to substantially lower energies in the near- and mid-infrared regions of the spectrum. The CTP offers both a high-information probe of optical frequency conductances in nanoscale junctions and a new, unique approach to controllably engineering tunable plasmon modes at infrared wavelengths.

Fractal nanoparticle plasmonics: the Cayley tree.

There has been strong, ongoing interest over the past decade in developing strategies to design and engineer materials with tailored optical properties. Fractal-like nanoparticles and films have long been known to possess a remarkably broad-band optical response and are potential nanoscale components for realizing spectrum-spanning optical effects. Here we examine the role of self-similarity in a fractal geometry for the design of plasmon line shapes. By computing and fabricating simple Cayley tree nanostructures of increasing fractal order N, we are able to identify the principle behind how the multimodal plasmon spectrum of this system develops as the fractal order is increased. With increasing N, the fractal structure acquires an increasing number of modes with certain degeneracies: these modes correspond to plasmon oscillations on the different length scales inside a fractal. As a result, fractals with large N exhibit broad, multipeaked spectra from plasmons with large degeneracy numbers. The Cayley tree serves as an example of a more general, fractal-based route for the design of structures and media with highly complex optical line shapes.