Date of Award

2024

Degree Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry

Department

Chemistry

First Advisor

Brett L. Lucht

Abstract

Scientific fields exploring topics such as DNA, RNA, proteins, and glycans have embraced the use of nanopores as a robust and reliable molecular sensor platform for sequencing and single molecule analysis. Solid-state nanopores show promise in expanding the sensing platform's capabilities towards proteomics and even the complex challenges of glycomics. Nanopores formed in thin films of silicon-rich silicon nitride represent a class of solid-state nanopores that not only provide a single molecule analysis platform capable of classifying glycans but also demonstrate the ability to be custom-tailored for specific analytes and measurements using covalent surface modifications. Surface modification on this class of nanopores has enabled researchers to gain control over some of the basic nanopore translocation physics and manipulate analyte translocation dynamics, enabling more information to be obtained from experiments. The work presented discusses the use of a photo-initiated hydrosilylation reaction to covalently modify silicon nitride nanopores, describes the development of a nanopore characterization method nanopores with a custom designed fluidic control apparatus, and highlights the application of silicon nitride nanopores in the analysis of synthetic glycans.

The hydrosilylation reaction has many mechanisms by which the reaction can occur, and chapter 2 highlights the assumptions that have been made to apply the reaction to nanopore surface modification. A form of the nanopore characterization method has been used in the past and has been hypothesized to take advantage of the nanopore dynamics mentioned above. Using CAD software and 3D printing, we designed and prototyped an apparatus to assist researchers in performing nanopore surface modification characterization experiments. Chapter 3 walks through the challenges of developing the method including conducting current measurements at a picoamp-nanoamp scale under electrolyte flow, EMI, 3D printing constraints, bubble management, and flow regulation. The apparatus and characterization method were validated by replicating results through the analysis of previously defined surfaces: non-modified bare silicon nitride, and surfaces modified with 4-pentenoic acid, and allylamine by photo-initiated hydrosilylation. Finally, chapter 4 demonstrated the application of silicon nitride nanopore sensors with the identification of synthetic glycans with the assistance of a machine learning analysis of the nanopore data.

G_v_pH_Analysis.txt (154 kB)
G v pH Analysis - Data Code for Chapter 3

BL_and_Event_Analysis.txt (80 kB)
BL and Event Analysis - Data Code for Chapter 4

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