Table Of ContentSpringer Theses
Recognizing Outstanding Ph.D. Research
Tian Lu
Nanomaterials
for Liquid
Chromatography
and Laser Desorption/
Ionization Mass
Spectrometry
Springer Theses
Recognizing Outstanding Ph.D. Research
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Tian Lu
Nanomaterials for Liquid
Chromatography and Laser
Desorption/Ionization Mass
Spectrometry
Doctoral Thesis accepted by
The Ohio State University, Columbus, USA
123
Author Supervisor
Dr. TianLu Prof.Susan V.Olesik
Analytical Department DepartmentofChemistryandBiochemistry
Ashland Inc. The OhioStateUniversity
Bridgewater, NJ Columbus
USA USA
ISSN 2190-5053 ISSN 2190-5061 (electronic)
ISBN 978-3-319-07748-2 ISBN 978-3-319-07749-9 (eBook)
DOI 10.1007/978-3-319-07749-9
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Parts of this thesis have been published in the following journal articles:
Lu, T.; Olesik, S. V. ‘‘Homogeneous Edge-Plane Carbon as Stationary Phase for
Reversed-Phase Liquid Chromatography’’ Anal. Chem. 2015, DOI: 10.1021/
ac503195r.
Lu,T.;Zewe,J.W.;Cevheri,N.;Olesik,S.V.‘‘FluorescentCarbonbyCovalently
Attaching a BODIPY Fluorophore’’ RSC Adv. 2014, 4, 62651.
Lu, T.; Olesik, S. V. ‘‘Electrospun Nanofibers as Substrates for Surface-Assisted
LaserDesorption/IonizationandMatrix-EnhancedSurface-AssistedLaserDesorp-
tion/Ionization Mass Spectrometry’’ Anal. Chem. 2013, 85, 4384.
Lu, T.; Olesik, S. V. ‘‘Electrospun Polyvinyl Alcohol Ultra-Thin Layer Chroma-
tography of Amino Acids’’ J. Chromatogr., B 2013, 912, 98.
This document is dedicated to my family
Supervisor’s Foreword
I would like to acknowledge the significant innovations of Tian Lu that are
highlighted within this dissertation.
This dissertation is broad sweeping in its scope spanning from chemical to
synthesistostate-of-the-artanalyticalchemistry.Majorimprovementsinultrathin
layer chromatography, surface-assisted laser desorption ionization (SALDI), and
matrix-assisted(ME-SALDI)massspectrometry.Inaddition,anedge-plane-based,
ordered carbon surface is highlighted that provides unique selectivity in liquid
chromatography. Electrospun polyvinyl alcohol (PVA) ultrathin layer chromato-
graphic (UTLC) plates were fabricated using in situ crosslinking electrospinning
technique. The efficiency on PVA plates was greatly improved compared to the
efficiency on silica HPTLC plates.
Electrospunpolymernanofibers(polyacrylonitrile,polyvinylalcohol,andSU-8
photoresist), and carbon nanofibers were used for the first time as substrates for
surface-assistedlaserdesorption/ionization(SALDI)andmatrixenhancedsurface-
assisted laser desorption/ionization (ME-SALDI) analyses. Mass spectra of
organic polymers with high signal/noise were observed. For example, polyethyl-
ene glycol with a molecular weight as high as 900,000 Da was successfully
detected using the carbon nanofibrous substrate, which is the highest molecular
weight that has been studied by SALDI to date. High quality polystyrene mass
spectrawereobtainedforthefirsttimeusingSALDInanofibrouspolyacrylonitrile
substrates.ME-SALDIshowedenhancedsignalfortheanalytesusingelectrospun
nanofibrous substrates compared to using a conventional stainless steel substrate.
The detection limit of 400 amol was achieved for angiotensin I using the carbon
nanofibrous ME-SALDI substrate.
Thisisexquisiteandgroundbreakingwork;IcongratulateDr.Luonthesuccess
that she has had to date.
Columbus, USA, May 2014 Prof. Susan V. Olesik
ix
Acknowledgments
First,Iwouldliketoexpressmygreatthankstomyadvisor,Dr.SusanOlesik,for
hercontinuoussupportformyPh.D.program.Herinspiringguidancehelpedmeto
make progress during my Ph.D. research. She also encouraged my own ideas and
different ways to solve problems.
I would like to extend my special thanks to Dr. Joe Zewe who started the
fluorescent carbon synthesis and worked closely with me on the project. He also
helpedmeontheoptimizationofthesolidphaseextractioncondition.Iwouldlike
to thank Prof. Minami Yoda and her group members for the suggestions on the
synthesis offluorescent carbon particles and providing the image of the particles.
IalsothanktheNationalScienceFoundationforprovidingthefundingtocomplete
this work.
I would like to thank all of the Olesik group members who gave me insightful
suggestions on my research and it was a pleasure to work with them.
Last but not least, I would like to thank my family members. Without their
support and encouragement this dissertation would not have been possible.
xi
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Concepts and Definitions in Chromatography. . . . . . . . . . . . . . 1
1.2 Stationary Phases in Liquid Chromatography . . . . . . . . . . . . . . 2
1.2.1 Stationary Phases in Normal-Phase Thin Layer
Chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.2 Carbon Stationary Phases in HPLC. . . . . . . . . . . . . . . . 6
1.3 Sorbents in Solid Phase Extraction . . . . . . . . . . . . . . . . . . . . . 8
1.4 Substrates for Laser Desorption/Ionization Mass
Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2 Electrospun Polyvinyl Alcohol Ultra-Thin Layer
Chromatography of Amino Acids. . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Electrospinning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.3 FITC Labeled Amino Acids. . . . . . . . . . . . . . . . . . . . . 16
2.2.4 Thin Layer Chromatography. . . . . . . . . . . . . . . . . . . . . 16
2.2.5 Instrumentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.1 Electrospinning for Optimization of PVA
Nanofibrous Mat Structure. . . . . . . . . . . . . . . . . . . . . . 17
2.3.2 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3.3 Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3.4 Separation of Amino Acids Using Ninhydrin
as Visualization Reagent . . . . . . . . . . . . . . . . . . . . . . . 25
2.3.5 Analysis of Aspartame in Diet Coke. . . . . . . . . . . . . . . 27
2.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
xiii
