With the emergence of Matrix Assisted Laser Desorption/Ionization-Time-of-flight as a tool for diagnosis of diseases via proteomics, there is an increasing need for greater sensitivity. Analysis of peptides by MALDI-TOF-MS is affected by sample formulation and spotting onto a MALDI target. This dissertation investigates a novel MALDI sample preparation technique, Induction Based Fluidics (IBF), for depositing precise volumes (pL to nL) of samples onto the target. We have seen that while using IBF, the induced electric field accompanying deposition enhances matrix crystallization yielding smaller crystals with more homogeneity, as compared to conventional manual micropipette (MP) depositions. An investigation of the signal-to-noise (S/N) for IBF deposition of tryptic digested Bovine Serum Albumin (BSA) showed a significant improvement in the signal-to-noise ratio for 0.5 and 0.25 pmol/µL BSA sample compared to equivalent MP depositions. The S/N enhancement for IBF and MP depositions of BSA were studied using à-cyano-4-hydroycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) matrices, and CHCA showed better results than DHB . The exciting results obtained by IBF prompted us to probe sample morphology more fully and to relate morphology to the detections level and hopefully, to increase the utility of MALDI-TOF-MS for detection of a larger range of peptides. Morphology results were correlated to sensitivity limits using both dispensing techniques. Because of dissimilar rates of evaporation, different or uneven deposition thickness, or crystal lattice morphology, discontinuous crystallization patterns were observed for MP depositions. However, IBF deposited samples occupied less planar area with uniform distribution of crystals, thereby reducing sample crystal heterogeneity and laborious hunt for a "sweet" or "hot" spot to produce high quality spectra. The application of IBF was extended to the tryptic digested BSA protein using peptide mass fingerprinting. IBF deposition resulted in a larger number of detectable peptides as well as higher sequence coverage as compared to equivalent MP depositions. In last few decades, advanced research and potential applications in the field of microelectronics have spurred interest in the development of reticulated doped polymer films. Bis (ethylenedioxy) tetrathiafulvalene (BEDO-TTF)/Polycarbonate (PC) films were synthesized and characterized for use in hand-held real time explosives sensors, capable of detecting nitro-based compounds (nitroaromatics, nitoamines and nitroesters), which are the main components of Improvised Explosive Devices or IEDs. Reticulated doped polymer films were prepared by exposing solid solutions of BEDO-TTF in PC to iodine to form conductive charge transfer complexes. The resulting films exhibited room temperature conductivities ranging from 6.33-90.4*10-5 S cm-1. The colored iodine complexes in the film were reduced by cyclic voltammetry yielding conductive, colorless, transparent films. Dielectric analysis (DEA) was used to probe relaxations in neat PC and BEDO-TTF/PC showed that BEDO-TTF plasticized the PC and decreased the glass transition temperature. Two secondary relaxations appeared in PC films, whereas the transitions merged in the doped film. DEA also revealed conductivity relaxations above 180°C, which were characterized by the electric modulus formalism and showed that BEDO-TTF increased the alternating current, (AC) conductivity in PC.

Matrix Assisted Laser Desorption Ionization–Time of Flight (MALDI-TOF) mass spectroscopy is used in the characterization of synthetic polymers. MALDI allows for determination of: modal, most probable peak (M P), molecular number average (MN), molecular weight average (MW), polydispersity (PD), and polymer spread (PSP). We evaluate a new sample preparation method using Induction Based Fluidics (IBF) to kinetically launch and direct nanoliter volumes to a target without contact. IBF offers signal improvement via field enhanced crystallization. This is the first study to discuss filed enhanced crystallization in MALDI sample preparation. IBF can increase signal/noise (S/N) and signal intensity for polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(ethylene glycol) (PEG) across a mass range of 2,500 to 92,000 Da showing more accurate PSP. Increases in S/N range up to: 279% for PS, 140% for PMMA, and 660% for PEG. Signal intensities increased up to: 438% for PS, 115% for PMMA, and 166% for PEG. Cross-polarization microscopy indicates dramatic morphology differences between IBF and micropipette. Finally, we speculate as to why IBF nanoliter depositions afford higher S/N values in experiments conducted in different instrumental configurations even without optimization. Next we sought to investigate whether nanoliter volumes of concentrated polar liquids and organic monomers launched to targets using IBF can be verified through the real time charge measurements. We show that using a nanoliter IBF dispensing device and nanocoulomb meter, charge measurements made on nanoliter drops in real time are correlated with the droplets surface area following Gauss’s Law. We infer the "induction only" formation of the double layer showing the ability to determine nanoliter volumes, nearly instantaneously, in real time. Implications are presented from these IBF measurement observations on improving/monitoring MALDI quantitation and its quality control. Polymer-dye interactions were further investigated using PMMA composites made from a polar metalloporphyrin [5-(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)-10,20-diphenylporphyrinato]zinc(II) (Zn(II)Bpin-DPP) in select weight %s (wt%s). Fluorescence spectroscopy has revealed that the porphyrin was well dispersed within the composite. Differential Scanning Calorimetry (DSC) showed that porphyrin acted as an antiplasticizer raising the glass transition (Tg) from 105 °C to 123 °C. Dielectric Analysis (DEA) was performed in the frequency range of 0.3 Hz to 100 kHz between -150 to 270 ⁰C. Permittivity (ε’), loss factor (ε’’) and dielectric response of beta (β), alpha beta (αβ), and conductivity relaxations were studied. Previous DEA data was limited to 190 ⁰C. This study brings analysis to 270 ⁰C which is start point for the first part of PMMA degradation. Thus forwarding DEA can be used to evaluate PMMA degradation. The electric modulus formalism is used to reveal the β and conductivity relaxations. The apparent activation energies (Ea) for the molecular relaxations are presented. AC (ζAC) and DC (ζDC) conductivity are also evaluated. Tan delta (δ), dissipation factor, evaluated between 1 Hz to 100 kHz was shown to increase with porphyrin loading although locally affected by free volume restriction. Havriliak-Negami (H-N) equation was fit using the complex electric modulus (M*) modified form and was performed on the conductivity region 160 to 190 ⁰C and degradation region 190 to 270 °C. Relaxations above the Tg were proven to be conductivity relaxations using four proofs. This is the first study to investigate PMMA degradation DEA with the complex electric modulus, M*, revealing a unique occurrence of increasing central relaxation times (s-1) and reducing electric loss modulus (M") frequency maxima (Hz) after the degradation temperature of 220 ⁰C was reached supporting current literature of the first of a two part degradation process that proceeds via end chain scission.