{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/78515"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/78515","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Development of Mass Spectrometry Based Methods and Sample Preparation Strategies for the Analysis of Pesticides, Hormones, Metals, and Biomarkers of Endocrine Disruption in the Environment","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["He, Ping; 0000-0002-7681-4110"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Colon, Luis","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018-10-26T02:54:40Z","date_published":"2018-10-26T02:54:40Z","updated_at":"2026-07-27T19:05:09Z","subjects":["analytical chemistry"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/78515","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Colon, Luis","Chemistry"]},{"key":"dc:creator","label":"Author","values":["He, Ping; 0000-0002-7681-4110"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2018-10-26T02:54:40Z","2018","2018-07-12 22:07:20"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation","Text"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["analytical chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/78515"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","Chromatographic separation coupled with mass spectrometric detection enabled analysis of trace contaminants in complex matrices. The introduction of liquid chromatography tandem mass spectrometry (LC-MS/MS) allowing for analysis of polar compounds in water samples without derivatization, while the gas chromatography tandem mass spectrometry (GC-MS/MS) as complementary for volatile and semi-volatile components. Inductively coupled plasma mass spectrometry (ICP-MS) is designed for simultaneous determination of metals, and by coupling with chromatography the speciation analysis could be achieved. Endocrine disrupting chemicals (EDCs), which include natural and synthetic hormones, pesticides, and many classes of compounds used in consumer products and industrial applications are constantly introduced in the aquatic environment from sewage treatment plant effluents, agricultural and livestock run-off, and industrial emissions. Many of these contaminants are present at very low concentrations (ng/L to µg/L) in the aquatic systems, but yet affect the metabolic, developmental, and reproductive functions in exposed fish and wildlife. The work in this thesis, aims to develop sensitive chromatography mass spectrometry based methods to quantify contaminants (pesticides, hormones, metals) in trace concentrations. An effective cross-species method to detect VTG in fish as biomarker of EDCs in the environment has been investigated using LC-MS/MS. Moreover, Oxi-ND-NH2 nanoparticle was introduced as a novel sorbent for peptides enrichment and clean-up before LC-MS/MS analysis.In Chapter 2, quantitative analysis using LC-MS/MS was developed for the detection of potential EDCs including estrogens, pesticides, and industrial chemicals. Scheduled selected reaction monitoring acquisition assured the optimum sensitivity of trace analysis. Electrospray positive and negative ionization were performed in single run by using wrong-way-round ionization at high pH condition. The validated method was applied to river water samples with results indicated that method suitable for monitoring potential EDCs in aquatic environment. A GC-MS/MS method was developed as complementary for organochlorine pesticides that not be able to analyzed by LC-MS/MS. Chapter 3 focuses on developing an analytical approach to assess the effects of EDCs at environmentally relevant concentrations and providing as a tool that will allow scientists and regulators to better assess the overall effects of mixtures of chemicals in contaminated environments. Vitellogenin (VTG) protein is a widely-used biomarker in fish for assessing exposure to EDCs, and is commonly measured using species-specific immunochemical techniques. In this study, we developed a LC-MS/MS method that can measure common peptides from digested VTG in multiple fish species. In the initial experiments using high resolution mass spectrometer, two peptides (ALHPELR and FIELIQLLR) were identified as common fragments in the digested VTG protein isolated from three different fish species (Pimephales promelas, Micropterus salmoides, and Fundulus heteroclitus). Then, a quantitative analysis using LC-MS/MS under selected reaction monitoring mode was developed for the detection of these two peptides in trypsin-digested plasma from female fish (positive control), estrogen-exposed male fish (test sample), and unexposed male fish (negative control) using two same species for identifying the common peptides (P. promelas, and M. salmoides) and one new species (Ameiurus nebulosus) that was not included during the selection of peptides. Results from this study demonstrate the potential of LC-MS/MS as an effective cross-species method to detect VTG in fish, which can be an alternative analytical technique for assessing endocrine disruption in multiple fish species.As working in the VTG project, we realized mass spectrometry based protein digests bioanalysis is challenging due to the presence of complex interferences from matrix unless analytes were selectively isolated and enriched. Therefore, in Chapter 4, phenylamine functionalized oxidized nanodiamond (Oxi-ND-NH2) was introduced as a novel dispersive solid-phase extraction (dSPE) sorbent for peptides enrichment and clean-up before LC-MS/MS analysis. Nanodiamond (ND) particles attract increasing attention as sorbent for sample clean-up because of their particularly stability, high surface area, and controllable functional groups. The Oxi-ND-NH2 is functionalized ND particles with additional phenylamine groups, allowing for extra interactions with analytes such as π-π interaction, electrostatic interaction, and hydrogen binding. As a proof of concept, five commercially available peptides were used to investigate the effectiveness of dSPE. To demonstrate developed method could be utilized in protein bioanalysis, digested fish plasma samples were analysed for targeted VTG biomarker peptides with additional dSPE clean-up to highlight the benefits and effectiveness of this sorbent in LC-MS/MS based bioanalysis workflow. Chapter 5 is about developing HPLC-ICP-MS method for the separation and quantification of arsenic species which can serve as a powerful tool for different applications. For this study, the focus was on the determination of: As III and As V (the most toxic forms of arsenic), DMA V and MMA V, which are the commonly seen metabolites of inorganic arsenic and considered less toxic. In other collaborated projects, the speciation of arsenic is necessary for investigating the potential role of the enzyme N-6 adenine-specific DNA methyltransferase 1 (N6AMT1) in arsenic-induced toxicity. Method has also been modified to be implemented in the undergraduate-level analytical chemistry laboratory."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Development of Mass Spectrometry Based Methods and Sample Preparation Strategies for the Analysis of Pesticides, Hormones, Metals, and Biomarkers of Endocrine Disruption in the Environment"]}]}],"canonical_facts":{"dc:contributor":["Colon, Luis","Chemistry"],"dc:creator":["He, Ping; 0000-0002-7681-4110"],"dc:date":["2018-10-26T02:54:40Z","2018","2018-07-12 22:07:20"],"dc:description":["Ph.D.","Chromatographic separation coupled with mass spectrometric detection enabled analysis of trace contaminants in complex matrices. The introduction of liquid chromatography tandem mass spectrometry (LC-MS/MS) allowing for analysis of polar compounds in water samples without derivatization, while the gas chromatography tandem mass spectrometry (GC-MS/MS) as complementary for volatile and semi-volatile components. Inductively coupled plasma mass spectrometry (ICP-MS) is designed for simultaneous determination of metals, and by coupling with chromatography the speciation analysis could be achieved. Endocrine disrupting chemicals (EDCs), which include natural and synthetic hormones, pesticides, and many classes of compounds used in consumer products and industrial applications are constantly introduced in the aquatic environment from sewage treatment plant effluents, agricultural and livestock run-off, and industrial emissions. Many of these contaminants are present at very low concentrations (ng/L to µg/L) in the aquatic systems, but yet affect the metabolic, developmental, and reproductive functions in exposed fish and wildlife. The work in this thesis, aims to develop sensitive chromatography mass spectrometry based methods to quantify contaminants (pesticides, hormones, metals) in trace concentrations. An effective cross-species method to detect VTG in fish as biomarker of EDCs in the environment has been investigated using LC-MS/MS. Moreover, Oxi-ND-NH2 nanoparticle was introduced as a novel sorbent for peptides enrichment and clean-up before LC-MS/MS analysis.In Chapter 2, quantitative analysis using LC-MS/MS was developed for the detection of potential EDCs including estrogens, pesticides, and industrial chemicals. Scheduled selected reaction monitoring acquisition assured the optimum sensitivity of trace analysis. Electrospray positive and negative ionization were performed in single run by using wrong-way-round ionization at high pH condition. The validated method was applied to river water samples with results indicated that method suitable for monitoring potential EDCs in aquatic environment. A GC-MS/MS method was developed as complementary for organochlorine pesticides that not be able to analyzed by LC-MS/MS. Chapter 3 focuses on developing an analytical approach to assess the effects of EDCs at environmentally relevant concentrations and providing as a tool that will allow scientists and regulators to better assess the overall effects of mixtures of chemicals in contaminated environments. Vitellogenin (VTG) protein is a widely-used biomarker in fish for assessing exposure to EDCs, and is commonly measured using species-specific immunochemical techniques. In this study, we developed a LC-MS/MS method that can measure common peptides from digested VTG in multiple fish species. In the initial experiments using high resolution mass spectrometer, two peptides (ALHPELR and FIELIQLLR) were identified as common fragments in the digested VTG protein isolated from three different fish species (Pimephales promelas, Micropterus salmoides, and Fundulus heteroclitus). Then, a quantitative analysis using LC-MS/MS under selected reaction monitoring mode was developed for the detection of these two peptides in trypsin-digested plasma from female fish (positive control), estrogen-exposed male fish (test sample), and unexposed male fish (negative control) using two same species for identifying the common peptides (P. promelas, and M. salmoides) and one new species (Ameiurus nebulosus) that was not included during the selection of peptides. Results from this study demonstrate the potential of LC-MS/MS as an effective cross-species method to detect VTG in fish, which can be an alternative analytical technique for assessing endocrine disruption in multiple fish species.As working in the VTG project, we realized mass spectrometry based protein digests bioanalysis is challenging due to the presence of complex interferences from matrix unless analytes were selectively isolated and enriched. Therefore, in Chapter 4, phenylamine functionalized oxidized nanodiamond (Oxi-ND-NH2) was introduced as a novel dispersive solid-phase extraction (dSPE) sorbent for peptides enrichment and clean-up before LC-MS/MS analysis. Nanodiamond (ND) particles attract increasing attention as sorbent for sample clean-up because of their particularly stability, high surface area, and controllable functional groups. The Oxi-ND-NH2 is functionalized ND particles with additional phenylamine groups, allowing for extra interactions with analytes such as π-π interaction, electrostatic interaction, and hydrogen binding. As a proof of concept, five commercially available peptides were used to investigate the effectiveness of dSPE. To demonstrate developed method could be utilized in protein bioanalysis, digested fish plasma samples were analysed for targeted VTG biomarker peptides with additional dSPE clean-up to highlight the benefits and effectiveness of this sorbent in LC-MS/MS based bioanalysis workflow. Chapter 5 is about developing HPLC-ICP-MS method for the separation and quantification of arsenic species which can serve as a powerful tool for different applications. For this study, the focus was on the determination of: As III and As V (the most toxic forms of arsenic), DMA V and MMA V, which are the commonly seen metabolites of inorganic arsenic and considered less toxic. In other collaborated projects, the speciation of arsenic is necessary for investigating the potential role of the enzyme N-6 adenine-specific DNA methyltransferase 1 (N6AMT1) in arsenic-induced toxicity. Method has also been modified to be implemented in the undergraduate-level analytical chemistry laboratory."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/78515"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["analytical chemistry"],"dc:title":["Development of Mass Spectrometry Based Methods and Sample Preparation Strategies for the Analysis of Pesticides, Hormones, Metals, and Biomarkers of Endocrine Disruption in the Environment"],"dc:type":["Dissertation","Text"]},"updated_at":"2026-07-27T19:05:09Z"}