Analytical Chemistry Commons^™

Rational Design Of Electrochemical Molecular Probes For Highly Selective And Long-Term Measurement In Vivo, Yue Wang, Li-Min Zhang, Yang Tian

Journal of Electrochemistry

Designing electrochemical interfaces for in vivo analysis of neurochemicals with high selectivity and long-term stability is vital for monitoring dynamic variation and dissecting the complex mechanisms of pathogenesis in living animals. This review focuses on the development of electrochemical interfaces based on rational design of molecular probes for in vivo measurement with high selectivity and high stability from three aspects: (1) Specific recognition probes were rationally designed and created to remarkably improve the selectivity of in vivo analysis in a complicated brain environment. (2) The Au-C≡C functionalized surface was developed to remarkably enhance the stability of molecular assembly, and employed …

Synthesis And Evaluation Of 11c-Labeled Triazolones As Probes For Imaging Fatty Acid Synthase Expression By Positron Emission Tomography, James M. Kelly, Thomas M. Jeitner, Nicole N. Waterhouse, Wenchao Qu, Ethan J. Linstad, Banafshe Samani, Clarence Williams Jr., Anastasia Nikolopoulou, Alejandro Amor-Coarasa, Stephen G. Dimagno, John W. Babich

Department of Chemistry: Faculty Publications

Cancer cells require lipids to fulfill energetic, proliferative, and signaling requirements. Even though these cells can take up exogenous fatty acids, the majority exhibit a dependency on de novo fatty acid synthesis. Fatty acid synthase (FASN) is the rate-limiting enzyme in this process. Expression and activity of FASN is elevated in multiple cancers, where it correlates with disease progression and poor prognosis. These observations have sparked interest in developing methods of detecting FASN expression in vivo. One promising approach is the imaging of radiolabeled molecular probes targeting FASN by positron emission tomography (PET). However, although [¹¹C]acetate uptake by …

Chemical Reversible Crosslinking Enables Measurement Of Rna 3d Distances And Alternative Conformations In Cells, Ryan Van Damme, Kongpan Li, Minjie Zhang, Jianhui Bai, Wilson H. Lee, Joseph D. Yesselman, Zhipeng Lu, Willem A. Velema

Department of Chemistry: Faculty Publications

Three-dimensional (3D) structures dictate the functions of RNA molecules in a wide variety of biological processes. However, direct determination of RNA 3D structures in vivo is difficult due to their large sizes, conformational heterogeneity, and dynamics. Here we present a method, Spatial 2′-Hydroxyl Acylation Reversible Crosslinking (SHARC), which uses chemical crosslinkers of defined lengths to measure distances between nucleotides in cellular RNA. Integrating crosslinking, exonuclease (exo) trimming, proximity ligation, and high throughput sequencing, SHARC enables transcriptome-wide tertiary structure contact maps at high accuracy and precision, revealing heterogeneous RNA structures and interactions. SHARC data provide constraints that improves Rosetta-based RNA 3D …

Decomposition Of Organic Peroxides And Hydrogen Peroxide By The Iron Thiolates And Related Complexes, Patrick H. Dussault, Andrew Olson

Department of Chemistry: Faculty Publications

Disclosed herein is a method of reducing or disproportionating peroxide, comprising combining an organic chalcogenide, an iron salt, and the peroxide in the presence of an additional reductant, which can be the organic chalcogenide. The method can be used to, e.g., prepare alcohols from peroxides and to disproportionate hydrogen peroxide into water and oxygen.

A Flexible Enzymeless Glucose Sensor Via Electrodepositing 3d Flower-Like Cos Onto Self-Supporting Graphene Tape Electrode, Jiang Li, Zuo-Peng Li, Yun-Feng Bai, Su-Xing Luo, Yong Guo, Ya-Yan Bao, Rong Li, Hai-Yan Liu, Feng Feng

Journal of Electrochemistry

Three-dimensional (3D) nanostructural Flower-like cobalt sulfide (CoS) on flexible self-supporting graphene tape electrode (GTE) with remarkably electrocatalytic activity toward glucose was successfully prepared by electrodeposition. Structural characterizations revealed that the electrodeposited CoS was highly dispersed on GTE as an active material. The fabricated binder-free and self-standing CoS/GTE shows a good linear response in the range of 0.025 ~ 1.0 mmol·L^-1, reaching a high glucose sensitivity value of 323.3 μA·(mmol·L ^-1)^-1·cm^-2 and a low detection limit of 8.5 μmol·L ^-1 (S/N = 3). Moreover, the as-prepared sensor was well applied for glucose …

Effects Of Long-Term Fluoride Exposure Are Associated With Oxidative Biochemistry Impairment And Global Proteomic Modulation, But Not Genotoxicity, In Parotid Glands Of Mice, Giza Hellen Nonato Mirandai, Leidiane Alencar De Oliveira Lima, Leonardo Oliveira Bittencourt, Sa´Vio Monteiro Dos Santos, Michel Platini Caldas De Souza, Lygia Sega Nogueira, Edivaldo Herculano Corrêa De Oliveira, Marta Chagas Monteir, Aline Dionizio, Aline Lima Leite, Juliano Pelim Pessan, Juliano Pelim Pessan, Marı´Lia Afonso Rabelo Buzalaf, Rafael Rodrigues Limai

Department of Chemistry: Faculty Publications

Fluoride has become widely used in dentistry because of its effectiveness in caries control. However, evidence indicates that excessive intake interferes with the metabolic processes of different tissues. Thus, this study aimed to investigate the effects of long-term exposure to F on the parotid salivary gland of mice, from the analysis of oxidative, proteomic and genotoxic parameters.

The animals received deionized water containing 0, 10 or 50 mg/L of F, as sodium fluoride, for 60 days. After, parotid glands were collected for analysis of oxidative biochemistry, global proteomic profile, genotoxicity assessment and histopathological analyses.

The results revealed that exposure to …

Materials And Methodologies For Spectroscopic And Optical Analytical Applications In Cultural Heritage Conservation Science, Lyndsay Nichole Kissell

Dissertations and Theses

The field of conservation science falls in the intersection of science and art. The work of conservation scientists may include any single subdiscipline of chemistry, though it is most commonly a highly interdisciplinary field taking skills from analytical, organic, and inorganic chemistry, as well as surface and materials science. The aims of conservation scientists are to answer questions about the production and aging of material cultural heritage. Knowing the materials used by an artist can lead to insight about the intentions of the object and knowing how those materials degrade will enable the use of preventative measures to ensure the …

Wastewater-Based Estimation Of Substances Discharged At The Rest Areas Along The State Highways In Kentucky, Katherine E. Gray, Eugene Shin, Tyler Whitt, Andrew Windhorst, Houston Hampton, Chris Delcher, Bikram Subedi

Posters-at-the-Capitol

The availability of licit and illicit stimulants and its adverse consequences on public health has emerged as a major drug threat to communities in the United States. Despite several drug-involved traffic incidents along the interstate highways, this report represents the first comprehensive and quantitative report of drugs discharged at the rest areas along the interstate highways. In this National Institute of Justice-funded study, the amount of several discharged drugs focusing on stimulants but also including opioids and prescription antipsychotics are being measured in raw wastewater collected from five rest areas and a truck servicing facility using a state-of-the-art mass …

Web-Based Platform For Analysis Of Rna Folding From High Throughput Chemical Probing Data, Christopher Jurich, Amir Brivanlou, Silvi Rouskin, Joseph D. Yesselman

Department of Chemistry: Faculty Publications

RNA structures play critical roles in regulating gene expression across all domains of life and viruses. Chemical probing methods coupled with massively parallel sequencing have revolutionized the RNA structure field by enabling the assessment of many structures in their native, physiological context. Previously, we developed Dimethyl-Sulfate-based Mutational Profiling and Sequencing (DMS-MaPseq), which uses DMS to label the Watson-Crick face of open and accessible adenine and cytosine bases in the RNA. We used this approach to determine the genome-wide structures of HIV-1 and SARS-CoV-2 in infected cells, which permitted uncovering new biology and identifying therapeutic targets. Due to the simplicity and …

Peptidomics Analysis Reveals Changes In Small Urinary Peptides In Patients With Interstitial Cystitis/Bladder Pain Syndrome, Md Shadman Ridwan Abid, Haowen Qiu, Bridget Tripp, Aline De Lima Leite, Heidi E. Roth, Jiri Adamec, Robert Powers, James W. Checco

Department of Chemistry: Faculty Publications

Interstitial cystitis/bladder pain syndrome (IC/BPS) is a chronic and debilitating pain disorder of the bladder and urinary tract with poorly understood etiology. A definitive diagnosis of IC/BPS can be challenging because many symptoms are shared with other urological disorders. An analysis of urine presents an attractive and non-invasive resource for monitoring and diagnosing IC/BPS. The antiproliferative factor (APF) peptide has been previously identified in the urine of IC/BPS patients and is a proposed biomarker for the disorder. Nevertheless, other small urinary peptides have remained uninvestigated in IC/BPS primarily because protein biomarker discovery efforts employ protocols that remove small endogenous peptides. …

Developing A New Treatment For Superficial Fungal Infection Using Antifungal Collagen-Hsaf Dressing, Jing Zhong, Xiayi Yan, Xin Zuo, Xuan Zhao, Jiahui Yang, Qin Dou, Lulu Peng, Yuxiang Zhu, Yichen Xiao, Zeran Bian, Dalian He, Qiushuang Xu, Stephen Wright, Yaoyao Li, Liangcheng Du, Yan Wang, Jin Yuan

Department of Chemistry: Faculty Publications

Fungal pathogens are common causes of superficial clinical infection. Their increasing drug resistance gradually makes existing antifungal drugs ineffective. Heat stable antifungal factor (HSAF) is a novel antifungal natural product with a unique structure. However, the application of HSAF has been hampered by very low yield in the current microbial producers and from extremely poor solubility in water and common solvents. In this study, we developed an effective mode of treatment applying HSAF to superficial fungal infections. The marine-derived Lysobacter enzymogenes YC36 contains the HSAF biosynthetic gene cluster, which we activated by the interspecific signaling molecule indole. An efficient extraction …

Sequential Assembly Of 1-D And 2-D Origami Arrays, Nathan Shin

Theses, Dissertations and Capstones

DNA origami, invented by Paul Rothemund in 2006, provides many possible routes for the synthesis of complex macromolecular assemblies. This project involves the creation of 1-D and 2-D arrays of cross origami to support the development of DNA detection devices by providing precise platforms for these devices. The M13 plasmid is the most commonly used scaffold in DNA nanotechnology, limiting the size and complexity of an individual DNA origami construct. However, by creating larger assemblies, the dimensions can be multiplied. For example, by alternating two different types of cross origami, optical reporters can be separated by 200 nm, which is …

Extending Plasma Proteome Coverage To Enable Biomarker Discovery, Jordan Bruce Burton

Wayne State University Dissertations

Two features make plasma a valued source of health information: First, plasma contains secreted proteins from all tissues in the body and can, therefore, provide information about the health status of all tissues. Second, plasma is available in large quantity using a minimally invasive procedure that is well tolerated. The status of plasma as a valued source of health information is matched by the difficulty in extracting proteome information from the samples. Using state of the art instrumentation a standard analysis of plasma yields quantitative information on approximately 300 proteins. Extreme fractionation strategies coupled with increased mass spectrometry time extends …

Chromatographic Studies Of Some Hormone And Metabolic Modulators Used For Doping In Sports, Ruth Marie Speidel

Online Theses and Dissertations

The World Anti-Doping Agency (WADA) is an international agency that monitors the use of Performance Enhancing Drugs (PEDs) in sports; their mission is “to lead a collaborative worldwide movement for doping-free sport” (Who We Are, 2022). For this mission, the WADA needs quick, sensitive, reproducible, and accurate methods for analyzing athletes’ biological fluids for possible PEDs. This research focuses on developing and validating simple, sensitive, rapid, and reliable gas chromatography- mass spectrometry (GC-MS) methods for the analysis of two hormone and metabolic modulators, toremifene and trimetazidine. Previously, there has been limited GC-MS methods used to analyze toremifene and trimetazidine. Quantification …

Bond Valence Sum Analysis On Compounds Prepared By Topochemical Manipulation, Yasmin Dayeh

All Capstone Projects

The Bond Valence theory of Brown (1978) has been extensively used to correlate metal oxidation state to coordination environment in solids. Although the bond valence sum (BVS) appears to be extremely useful to coordination chemists, it has not often been applied as an alternative measure of refinement quality. In this work, previously reported six layered perovskite compounds including, RbLaNb2O7, Rb2LaNb2O7, Rb2SxLaNb2O7 (x ≤ 0.8), NaLaNb2O7, (Cs2Cl)LaNb2O7, and (FeCl)LaNb2O7, that have been prepared by topochemical manipulation and their structures have been determined by Rietveld refinements were analyzed. Our focus was to explore whether the determination of oxidation state using the bond …

Development And Applications Of Touch Chemistry Biometrics Analysis Of Latent Fingermarks By Maldi-Ms, Cameron M. Longo

Legacy Theses & Dissertations (2009 - 2024)

Fingerprint evidence has long been a pillar of forensic science and has been used for over a century as a means of identifying an individual. This is accomplished through the comparison of friction ridge patterns, which are inherently unique to each individual, and the practice of visualizing fingerprints and comparing them has become a well-studied field. While these techniques have been optimized and improved over time, they generally rely only on the physical pattern to provide information about the donor, and not the content of the fingerprint material itself. In the modern era, steps have been made to extract from …

Electrochemistry Of Bubbles: Developing New Sensors, Promoting Gas Evolution Reactions, And Extraction Of Rare Earth Elements, Ruchiranga R. Ranaweera

Wayne State University Dissertations

This dissertation presents new analytical, electrocatalysis, and separation strategies that utilize bubble behaviors in different electrochemical systems. The first part of this dissertation focuses on the method development for PFAS preconcentration and detection. First, we present the bubble-nucleation-based electrochemical method for the selective and sensitive detection of surfactants. Our method utilizes the high surface activity of surfactant analytes to affect the electrochemical bubble nucleation and then transduces the change in nucleation condition to an electrochemical signal for determining the surfactant concentration. Using this method, we demonstrate the quantitation of perfluorinated surfactants in water, a group of emerging environmental contaminants, with …

Microfluidic Thermal Gel Electrophoresis For Native Protein Analysis, Shakila Hasanthika Peli Thanthri

Wayne State University Dissertations

Proteins must be in their native states to carry out their intended biological functions. Native protein structure requires that proteins be folded into the correct conformations and possess the necessary post-translational modifications (PTMs). These higher-order structures are critical to ensuring that proteins are biologically active and properly interact with neighboring molecules. However, assessing folding conformations and modified protein variants is challenging, and routine sample validation techniques like polyacrylamide gel electrophoresis (PAGE) are not capable of analyzing higher-order structures. Gradient PAGE gels can determine the molecular weight of proteins over a wide mass range, but protein separation resolutions are poor because …

Building Tools For Improved Modulation Of The Human Gabaa Receptor, A Central Nervous System Target For The Treatment Of Anxiety, Garrett Edward Zinck

Theses and Dissertations--Pharmacy

In the U.S., anxiety is recognized as an increasing range of mentally and physically debilitating psychiatric health disorders with significant economic repercussions. Over the last 20 years, several novel anti-anxiety therapies have entered the drug development pipeline, but none have made it to market.

The work in this dissertation focused on structurally modifying valerenic acid (VA), a structurally unique carboxylated sesquiterpene acid found in Valeriana officinalis. VA is putatively reported to have allosteric modulatory activity of the human GABA_A receptor, a ligand-gated ion channel responsible for attenuating neurotransmissions. Structural modeling of VA’s GABA_A receptor interaction suggests that …

Investigating The Physical Stability Of Amorphous Pharmaceutical Formulations, Travis W. Jarrells

Theses and Dissertations--Pharmacy

Amorphous formulations, including amorphous solid dispersions (ASDs), consisting of the active pharmaceutical ingredient (API) intimately mixed in a polymeric matrix, are an attractive formulation approach to improve drug delivery, dissolution, and solubility. However, an amorphous API in an ASD is in a higher energy state compared to the crystalline drug and results in most ASDs being inherently unstable. The polymer helps to stabilize the amorphous drug against crystallization such that the resulting homogenous mixture maintains its solubility advantage relative to the crystalline form. One challenge of ASDs is that the presence of impurities including crystals or residual solvent, variations in …

A Study Of The Analysis Of Hemp-Derived Oil Products: Development Of A Method For The Analysis Of Phytocannabinoids In Medicinal Products, Erin Johnson

Theses and Dissertations--Pharmacology and Nutritional Sciences

Human interactions with cannabis have a history spanning millennia as a source of fiber, food, and medicine. The plant came across Asia, Europe, and Africa with the movements of people and travelers eventually coming to the Americas with European explorers. In colonizing North America, cannabis fiber was key to the production of canvas and ropes for ships. Although fiber was the driver for cannabis production in the United States, medicinal uses were prevalent and propelled the eventual regulations. The Pure Food and Drug Act of 1906 mandated accurate labeling on drugs such as cannabis followed by the Marihuana Tax Act …

Metabolomics Reveal Size-Dependent Impacts Of Cerium Oxide Nanoparticles On Grains Of Barley (Hordeum Vulgare L.), Naum Jepkemei Kirwa

Graduate Theses/Dissertations

Plants are exposed to emerging contaminants including nanoparticles, due to the novel but wide uses of these materials. However, researchers have shown contradicting effects of CeO₂-NPs on barley grains with focus mostly on concentration effects and not sizes of these CeO₂-NPs. Therefore, this study aimed at comparing the effects of 0nm (control), 8nm, and 40nm (250 mg CeO₂-NPs/kg soil) on the metabolite profile of barley grains. GC-FID and GC-QTOF-MS were used to measure fatty acid contents and metabolomic changes respectively. GC-FID analysis revealed that palmitic acid, oleic acid, linoleic acid, and the total fatty …

Development Of A New Spe Uplc–Ms/Ms Method For Extraction And Quantitation Of Toluene Diamine On Gloves Following Toluene Diisocyanate Exposure, Asma Daoud, Pierre-Luc Cloutier, Sébastien Gagné, Livain Breau, Jacques Lesage

Études primaires

Rationale

Toluene diisocyanate (TDI) is a highly reactive isocyanate commonly used as a mixture of 2,4- and 2,6- isomers in the production of flexible foams. Exposure to TDI occurs primarily through vapour inhalation in workplaces where TDI is produced or used, but dermal exposure is also possible during some tasks. To ensure workplace safety, accurate monitoring of TDI and toluene diamine (TDA) levels is required. Methods of quantifying field effectiveness of gloves in preventing dermal exposure have not been established. Therefore, there is a need to develop a new practical method for assessing glove effectiveness for TDI/TDA.

Method

A new …

Development Of A Chromatographic Method To Authenticate Aspirin Brands, Megan Guetzloff

Electronic Theses and Dissertations

Counterfeit pharmaceuticals pose a threat to society that can include inaccurate amounts of the active pharmaceutical ingredient (API), no API, or containing off-target compounds. For example, there are many recent examples of counterfeit pharmaceuticals containing potentially lethal doses (> 2 mg) of fentanyl (i.e., a synthetic opioid). Current measures to combat illicit pharmaceuticals (e.g., unique packaging and product serialization) have merit, however with evolved technologies, counterfeiters can relatively easily simulate these measures and continue to distribute illicit pharmaceuticals. The only accurate way to definitively determine that a suspected counterfeit is, in fact, counterfeit is advanced chemical analysis. However, current methods …

Purification And Activity Assay Optimization Of Bacterial Catalase From Psychrobacter Koprana, Sydney Willis

Honors Program Theses

To date, catalase protein from bacterial species is not the most widely used commercial catalase. Catalase, the enzyme that breaks down hydrogen peroxide in most living organisms, is an invaluable enzyme in the food, agriculture, and pharmaceutical industries. In 2019, a novel species of a psychrotolerant bacterium was discovered in Cold Harbor, NY. This species, Psychrobacter koprana, exhibits highly active catalase. Preliminary data from activity assays demonstrates that P. koprana catalase has the same activity as commercially available catalase. After purification and activity assay optimization, the activity of this catalase has the potential to be more active than other easily …

Trends In Biomedical Analysis Of Red Blood Cells – Raman Spectroscopy Against Other Spectroscopic, Microscopic And Classical Techniques, Jakub Dybas, Fatih Celal Alcicek, Aleksandra Wajda, Magdalena Kaczmarska, Anna Zimna, Katarzyna Bulat, Aneta Blat, Tetiana Stepanenko, Tasnim Mohaissen, Ewa Szczesny-Malysiak, David Perez-Guaita, Bayden R. Wood, Katarzyna Maria Marzec

Articles

Application of modern and innovative spectroscopic and microscopic approaches to biomedical analysis opens new horizons and sheds new light on many unexplored scientific territories. In this review, we critically summarize up-to-date Raman-based methodologies for red blood cells (RBCs) analysis used in biology and medicine, and compare them with both classical, as well as other spectroscopic and microscopic approaches. The main emphasis is placed on the advantages, disadvantages and capabilities of each technique for detection of RBC deteriorations and RBC-related diseases. Although currently used classical techniques of medical analysts serve as a gold standard for clinicians in diagnosis of erythropathies, they …

Development Of Nanodisc Affinity Capillary Electrophoresis To Study The Interaction Of Giα Protein With Cell Membranes, Bethany R. Emeigh

Graduate Student Theses, Dissertations, & Professional Papers

Guanine nucleotide-binding proteins, or G-proteins, are crucial to cell signaling by acting as molecular switches through interactions with membrane-bound receptors. G-proteins have become of greater interest due to the possibility of novel drug targets. The G-protein alpha subunit, Gα, binds GTP before localizing to the membrane to interact with other G-protein subunits and G-protein-coupled receptors (GPCRs). Gi lacks a hydrophobic region to promote localization to the membrane, but a co-translational lipidation of the N-terminal residue stabilizes this interaction.

Protein interactions with biological membranes are challenging to study due to the complex structure of membranes and the often-limited quantities of the …

Instrumental Analysis, David T. Harvey

Chemistry & Biochemistry Faculty Publications

Instrumental analysis is a field of analytical chemistry that investigates analytes using scientific instruments.

Characterization Of Nanoparticles Using Inductively-Coupled Plasma Mass Spectrometry, Jabez D. Campbell

Graduate Theses/Dissertations

Nanomaterials are a relatively new class of materials that have many applications which span a wide host of fields from medical products to consumer products. The possible compositions and forms of nanomaterials are just as varied as the applications. Therefore, a versatile characterization method is needed for researchers and regulators alike to ensure nanomaterials are properly used. Single Particle Inductively Coupled Plasma Mass Spectrometry (SP-ICP-MS) is a functional method that could fill the characterization need in the nanomaterial research field. Using data from both SP-ICP-MS tests and data from literature established characterization methods, the viability of making SP-ICP-MS the standard …

Optimizing The Fluorescent Quantum Yield Of Carbon Dots, Megan B. Prado

Graduate Theses/Dissertations

Carbon dots (CDs) are a subclass of carbon nanomaterials that exhibit unique properties of fluorescence, photostability, low toxicity, and biocompatibility. These unique properties have enabled numerous applications including biosensing, heavy-metal detection, and pH-sensing, among others. Their optical properties can be modified via doping to produce increasingly fluorescent CDs after appropriate purification. Herein, doped CDs were synthesized in four bottom-up methods for comparison using sucrose or citric acid as carbon precursors. Varying hetero-atom dopants (N, S, B) were used in differing molar ratios. The pH-dependent fluorescence and fluorescent quantum yield (QY) were measured for each sample. Characterization was conducted using Fourier-Transform …