Modulating unimolecular charge transfer by exciting bridge vibrations.

Ultrafast UV-vibrational spectroscopy was used to investigate how vibrational excitation of the bridge changes photoinduced electron transfer between donor (dimethylaniline) and acceptor (anthracene) moieties bridged by a guanosine-cytidine base pair (GC). The charge-separated (CS) state yield is found to be lowered by high-frequency bridge mode excitation. The effect is linked to a dynamic modulation of the donor-acceptor coupling interaction by weakening of H-bonding and/or by disruption of the bridging base-pair planarity.

Phase transfer catalysts drive diverse organic solvent solubility of single-walled carbon nanotubes helically wrapped by ionic, semiconducting polymers.

Use of phase transfer catalysts such as 18-crown-6 enables ionic, linear conjugated poly[2,6-{1,5-bis(3-propoxysulfonicacidsodiumsalt)}naphthylene]ethynylene (PNES) to efficiently disperse single-walled carbon nanotubes (SWNTs) in multiple organic solvents under standard ultrasonication methods. Steady-state electronic absorption spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM) reveal that these SWNT suspensions are composed almost exclusively of individualized tubes. High-resolution TEM and AFM data show that the interaction of PNES with SWNTs in both protic and aprotic organic solvents provides a self-assembled superstructure in which a PNES monolayer helically wraps the nanotube surface with periodic and constant morphology (observed helical pitch length = 10 ± 2 nm); time-dependent examination of these suspensions indicates that these structures persist in solution over periods that span at least several months. Pump-probe transient absorption spectroscopy reveals that the excited state lifetimes and exciton binding energies of these well-defined nanotube-semiconducting polymer hybrid structures remain unchanged relative to analogous benchmark data acquired previously for standard sodium dodecylsulfate (SDS)-SWNT suspensions, regardless of solvent. These results demonstrate that the use of phase transfer catalysts with ionic semiconducting polymers that helically wrap SWNTs provide well-defined structures that solubulize SWNTs in a wide range of organic solvents while preserving critical nanotube semiconducting and conducting properties.

State Political Parties in American Politics: Innovation and Integration in the Party System

What role do state party organizations play in twenty-first century American politics? What is the nature of the relationship between the state and national party organizations in contemporary elections? These questions frame the three studies presented in this dissertation. More specifically, I examine the organizational development of the state party organizations and the strategic interactions and connections between the state and national party organizations in contemporary elections.

In the first empirical chapter, I argue that the Internet Age represents a significant transitional period for state party organizations. Using data collected from surveys of state party leaders, this chapter reevaluates and updates existing theories of party organizational strength and demonstrates the importance of new indicators of party technological capacity to our understanding of party organizational development in the early twenty-first century. In the second chapter, I ask whether the national parties utilize different strategies in deciding how to allocate resources to state parties through fund transfers and through the 50-state-strategy party-building programs that both the Democratic and Republican National Committees advertised during the 2010 elections. Analyzing data collected from my 2011 state party survey and party-fund-transfer data collected from the Federal Election Commission, I find that the national parties considered a combination of state and national electoral concerns in directing assistance to the state parties through their 50-state strategies, as opposed to the strict battleground-state strategy that explains party fund transfers. In my last chapter, I examine the relationships between platforms issued by Democratic and Republican state and national parties and the strategic considerations that explain why state platforms vary in their degree of similarity to the national platform. I analyze an extensive platform dataset, using cluster analysis and document similarity measures to compare platform content across the 1952 to 2014 period. The analysis shows that, as a group, Democratic and Republican state platforms exhibit greater intra-party homogeneity and inter-party heterogeneity starting in the early 1990s, and state-national platform similarity is higher in states that are key players in presidential elections, among other factors. Together, these three studies demonstrate the significance of the state party organizations and the state-national party partnership in contemporary politics.