Bennet, Kevin E.

A novel multi-waveform FSCV (M-FSCV) developed for characterizing adsorption/desorption kinetics of neurotransmitters.

Defining the pathogenesis of renal osteodystrophy (ROD) and its treatment efficacy are difficult, since many factors potentially affect bone quality. In this study, confocal Raman microscopy and parallel statistical analysis were used to identify differences in bone composition between healthy and ROD bone tissues through direct visualization of three main compositional parametric ratios, namely, calcium content, mineral-to-matrix, and carbonate-to-matrix. Besides the substantially lower values found in ROD specimens for these representative ratios, an obvious accumulation of phenylalanine is Raman spectroscopically observed for the first time in ROD samples and reported here. Thus, elevated phenylalanine could also be considered as an indicator of the disease. Since the image results are based on tens of thousands of spectra per sample, not only are the average ratios statistically significantly different for normal and ROD bone, but the method is clearly powerful in distinguishing between the two types of samples. Furthermore, the statistical outcomes demonstrate that only a relatively small number of spectra need to be recorded in order to classify the samples. This work thus opens the possibility of future development of in vivo Raman sensors for assessment of bone structure, remodeling, and mineralization, where different biomarkers are simultaneously detected with unprecedented accuracy.

A combined theoretical and experimental analysis of dopamine (DA) is presented in this work with the objective of achieving more accurate detection and monitoring of this neurotransmitter at very low concentrations, specific to physiological levels. Surface-enhanced Raman spectroscopy on silver nanoparticles was employed for recording DA concentrations as low as 10−11 molar. Quantum chemical density functional calculations were carried out using Gaussian-09 analytical suite software. Relatively good agreement between the simulated and experimentally determined results indicates the presence of different DA molecular forms, such as uncharged DA±, anionic DA−, and dopaminequinone. Disappearance of the strongest bands of dopamine around 750 cm−1 and 790 cm−1, which suggests its adsorption onto the metallic surface, is not only consistent with all of these DA configurations, but also provides additional information about the analyte’s redox process and voltammetric detection. On the other hand, occurrence of the abovementioned Raman lines could indicate the formation of multilayers of DA or its presence in a cationic DA+ form. Thus, through coordinated experiment and theory, valuable insights into changes observed in the vibrational signatures of this important neurotransmitter can be achieved for a better understanding of its detection at physiological levels, which is crucial if further optovoltammetric medical device development is envisioned.

A simple, and yet robust, high pass filter is designed to remove non-linear background drift in fast scan cyclic voltammetry.

In an effort to determine the chronic stability, sensitivity, and thus the potential viability of various neurochemical recording electrode designs and compositions, we have developed a custom device called the Voltammetry Instrument for Neurochemical Applications (VINA). Here, we describe the design of the VINA and initial testing of its functionality for prototype neurochemical sensing electrodes. The VINA consists of multiple electrode fixtures, a flowing electrolyte bath, associated reservoirs, peristaltic pump, voltage waveform generator, data acquisition hardware, and system software written in National Instrument’s LabVIEW. The operation of VINA was demonstrated on a set of boron-doped diamond neurochemical recording electrodes, which were subjected to an applied waveform for a period of eighteen days. Each electrode’s cyclic voltammograms (CVs) were recorded, and sensitivity calibration to dopamine (DA) was performed. Results showed an initial decline with subsequent stabilization in the CV current measured during the voltammetric sweep, corresponding closely with changes in electrode sensitivity to DA. The VINA has demonstrated itself as a useful tool for the characterization of electrode stability and chronic electrochemical performance.

Combined theoretical and experimental analysis of serotonin by quantum chemical density functional calculations and surface-enhanced Raman spectroscopy, respectively, is presented in this work to better understand phenomena related to this neurotransmitter’s detection and monitoring at very low concentrations specific to physiological levels. In addition to the successful ultrasensitive analyte detection on silver nanoparticles for concentrations as low as 10−11 molar, the relatively good agreement between the simulated and experimentally determined results indicates the presence of all serotonin molecular forms, such as neutral, ionic, and those oxidized through redox reactions. Obvious structural molecular deformations such as bending of lateral amino chains are observed for both ionic and oxidized forms. Not only does this combined approach reveal more probable adsorption of serotonin into the silver surface through hydroxyl/oxygen sites than through NH/nitrogen sites, but also that it does so predominantly in its neutral (reduced) form, somewhat less so in its ionic forms, and much less in its oxidized forms. If the development of opto-voltammetric biosensors and their effective implementation is envisioned for the future, this study provides some needed scientific background for comprehending changes in the vibrational signatures of this important neurotransmitter.

In this study, we present a comprehensive investigation of graphene’s optical and conductive properties using confocal Raman and a Drude model. A comparative analysis between experimental findings and theoretical predictions of the material’s changes and improvements as it transitioned from three-dimensional graphite is also presented and discussed. Besides spectral recording by Raman, which reveals whether there is a single, a few, or multi-layers of graphene, the confocal Raman mapping allows for distinction of such domains and a direct visualization of material inhomogeneity. Drude model employment in the analysis of the far-infrared transmittance measurements demonstrates a distinct increase of the material’s conductivity with dimensionality reduction. Other particularly important material characteristics, including carrier concentration and time constant, were also determined using this model and presented here. Furthermore, the detection of micromolar concentration of dopamine on graphene surfaces not only proves that the Raman technique facilitates ultrasensitive chemical detection of analytes, besides offering high information content about the biomaterial under study, but also that carbon-based materials are biocompatible and favorable micro-environments for such detection. Such information is valuable for the development of bio-medical sensors, which is the main application envisioned for this analysis.