Semester

Summer

Date of Graduation

2014

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Chemistry

Committee Chair

Fred L. King

Committee Co-Chair

Patrick S. Callery

Committee Member

Ronald B. Smart

Committee Member

Bjorn C.G. Soderberg

Committee Member

Stephen J. Valentine

Abstract

Microfluidics continues to be of interest for analyzing chemical and biological samples because of the disposability, portability, low sample consumption, fast analysis time, and parallel analysis potential for multiple samples in a single device. To improve microfluidic device functionality, integrated systems-nanofluidic/microfluidic interfaces (NMIs) have been fabricated for concentrating samples and performing as molecular gates. Ion current rectification has been confirmed in NMI with an asymmetric system. In chapter 2, the asymmetry of the NMI is systematically altered by varying the inner diameter of the nanocapillary membrane (NCM) reservoir, and the current rectification factor is observed to increase as the inner diameter of NCM reservoir increases. The data provide a new approach to tune the ion current rectification of NMIs and strengthen the fundamental knowledge of how these devices function.;Glow discharge mass spectrometry (GDMS) is a well-established technique for the direct analysis of elements in solid samples. The introduction of pulsed glow discharge makes the internal energy of GD plasma tunable so that the specific desired ion signal profiles can be obtained and used for chemical speciation. For example, the elemental, structural, and molecular information of organic molecules have been obtained nearly simultaneously using glow discharge time-of-flight mass spectrometry (GDToFMS) coupled with gas chromatography. With careful control of operating parameters of GDToFMS, specific cluster ions or ion abundance ratios can be used for speciation of chromium oxides, manganese oxides, and iron oxides.;Chapters 3 and 4 focus on extending the application of pulsed glow discharge time-of-flight mass spectrometry for chemical speciation. Chapter 3 is the analysis of cysteine using pulsed glow discharge time-of-flight mass spectrometry. The characteristic fragment ion at m/z 76 is used for the quantitative analysis for cysteine. The calibration curve for cysteine standards obtained exhibits good linearity. In chapter 4, the application of pulsed glow discharge mass spectrometry is extended to direct NbxOy speciation. The effect of variations in temporal and spatial sampling along with variations in operating power on analyte ion signal distributions are studied and discussed. Under optimized conditions, the differentiation of three niobium oxides is achieved by comparison of ion abundance ratios.

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