Analytical Chemistry Commons^™

Design And Application Of Smart Systems To Address Analytical Problems, Lucas B. Ayres

All Dissertations

This dissertation is a multidisciplinary effort that integrates low-cost analytical instrumentation, redox chemistry, and artificial intelligence to overcome existing limitations in the fields of wearable sensing technology, Deep Eutectic Solvents (DES), and antioxidant chemistry. The overall goal behind each implemented strategy is to enhance the accuracy, efficiency, and accessibility of analytical processes and technologies. A general overview of the thesis, along with the research outcomes is included in Chapter One. The theoretical framework of this dissertation is presented in Chapter Two. Chapter Three describes the development of a wearable platform (sensor and instrumentation) to rapidly detect (~20 minutes) S. aureus …

Electrochemical Advanced Treatment Of Desulfurization Wastewater From Coal-Fired Power Plants, Ju-Cai Wei, Juan Yi, Xu Wu

Journal of Electrochemistry

Zero-emission of desulfurization wastewater is one of the main demands for coal-fired power plants. As typical high salinity wastewater, it is hard to purify the desulfurization wastewater from coal-fired power plants through traditional physicochemical treatment or biochemical treatment, e.g., COD and Cl^–. A high concentration of Cl^– ion in desulfurization wastewater restricts wastewater reuse and zero-emission. Electrochemical technology is an attractive method for high salinity wastewater zero-emission, which provides a versatile, efficient, cost-effective, easily automatable, and clean industrial process. For advanced treatment of effluent after triple box process treatment in power plants, this paper reports an electrochemical …

X-Ray Fluorescence Analysis Of Historic Art Paint Pigments, Sofia A. Stirpe, Juergen Thieme

Binghamton University Undergraduate Journal

Utilizing synchrotron radiation, X-ray fluorescence (XRF) microscopy enables researchers to deduce the elemental composition of paint pigments with a higher sensitivity and resolution than that of lab-based XRF instruments. With this information, art historians can date paintings by examining the elemental makeup of paint pigments and the time periods in which they were used. One painting, Christ and the Woman Taken in Adultery, has been duplicated by Pieter Brueghel the Younger and other artists, leading to confusion over which artworks are Brueghel masterpieces or copies by other artists. Art historian Maurizio Seracini, retaining a painting that could be assigned …

Comparison Of Atmospheric Pressure Chemical Ionization And Electrospray Ionization Mass Spectrometry For The Direct Analysis Of Hops Bittering Compounds, Chhiring Sherpa

Masters Theses

Hops acids are essential components in the beer brewing process containing alpha acids (α-acids) and beta acids (β-acids) as the major hops bittering compounds. Quantifying these acids is vital for quality control and determining bitterness levels and hops variety profiles. Current industry standards, like High-Performance Liquid Chromatography with Ultraviolet detection (HPLC-UV) and Ultraviolet Spectroscopy (UV-Vis), though effective, are time-consuming and solvent-intensive, providing incomplete information.

This research introduces a novel method using mass spectrometry with atmospheric pressure chemical ionization (APCI-MS) to analyze hops bittering acids without chromatographic separations. This approach offers rapid analysis, high throughput, and eco-friendliness.

Comparison with direct electrospray …

Diagnosing Discharge Events Within A Novel Miniature Simplified Coaxial Ion Trap Mass Analyzer, David Virgil Sirbescu-Stanley

Masters Theses

Mass spectrometry is a technique that organizes material samples by mass to reveal their chemical composition by forming a spectrum. Since their invention, ion trap mass spectrometers have undergone significant enhancements. This work, funded by the National Science Foundation and in collaboration with Brigham Young University, the Simplified Coaxial Ion Trap (SCIT), attempts to simplify ion trap geometry and combine three ion traps into one device. Successful demonstration of the SCIT functionality could reduce costs, reduce manufacturing complexity, and shrink total instrument volume. At the same time, trapping capacity and analytical efficiency will be increased. However, as discussed within, challenges …

Accurate Estimation Of Ethanol Content In Fruit Juices Using Cielab Color Space And Chemometrics Via Smartphone-Based Digital Image Colorimetry, Chairul Ichsan, Yasir Amrulloh, Desti Erviana

Makara Journal of Science

This study aims to investigate the optimal color space and chemometric technique for digital image colorimetry to determine ethanol content (% v/v) in apple, orange, and grape juices, using potassium dichromate (K₂Cr₂O₇) under acidic conditions. The accuracy of colorimetric–chemometric integration across various color spaces (RGB, HSV, CIELab, CMYK, CIELuv, CIEXYZ, and CIELch) was benchmarked against UV–Vis spectrophotometry using metrics such as coefficient of determination (R²), mean absolute percentage error (MAPE), and root–mean–squared error (RMSE). Various chemometric techniques (PLS, PCR, MLR, multivariable–SVR, and multivariable NN regression) were evaluated. Results demonstrate that combining the CIELab color …

Advancements In Characterization Of Ancient Potteries From Southeast Asia: A Review Of Analytical Techniques, Chitnarong Sirisathitkul

Makara Journal of Science

Ancient potteries offer valuable information regarding technological advancements, life dynamics, cultural diversity, and trade routes in the past. Earthenware, stoneware, and porcelain from Southeast Asia have been characterized using several analytical techniques, as reviewed in this article. Fluorescent and diffracted X-rays give rise to elemental and phase compositions, respectively. Examination of molecular bonds requires vibrational spectroscopy, which is useful for the identification of organic materials in ancient potteries. With the advent of portable X-ray fluorescence and Raman spectrometry, on-site analysis of archeological ceramics is now possible. For in-depth analysis, synchrotron light sources can provide new insights into artifacts through X-ray …

The Determination Of Pzc And Differential Capacitance Curve Of Platinum-Alkaline Polymer Electrolyte Interfaces, Chen-Xi Liu, Ze-Ping Zou, Mei-Xue Hu, Yu Ding, Yu Gu, Shuai Liu, Wen-Jing Nan, Yi-Chang Ma, Zhao-Bin Chen, Dong-Ping Zhan, Qiu-Gen Zhang, Lin Zhuang, Jia-Wei Yan, Bing-Wei Mao

Journal of Electrochemistry

Alkaline polymer electrolyte (APE) is the core component of modern alkaline hydrogen and oxygen fuel cells, and its single ion conductor nature makes the "electrode/APE" interfaces different from the conventional "electrode/solution" interfaces in terms of ion distribution, electrical double layer structure and polarization behavior. Due to the complexity of the APE and the associated solid-solid interfaces, fundamental investigations are challenging and deeper understanding of the structures and properties of such interfaces is in the infant stage. In this work, we aim to investigate the double layer structure from the aspects of differential capacitance curve and potential of zero charge (PZC) …

Micropatterning And Functionalization Of Single Layer Graphene: Tuning Its Electron Transport Properties, Miao-Miao Cui, Lian-Huan Han, Lan-Ping Zeng, Jia-Yao Guo, Wei-Ying Song, Chuan Liu, Yuan-Fei Wu, Shi-Yi Luo, Yun-Hua Liu, Dong-Ping Zhan

Journal of Electrochemistry

As a promising 2D material, graphene exhibits excellent physical properties including single-atom-scale thickness and remarkably high charge carrier mobility. However, its semi-metallic nature with a zero bandgap poses challenges for its application in high-performance field-effect transistors (FETs). In order to overcome these limitations, various approaches have been explored to modulate graphene's bandgap, including nanoscale confinement, external field induction, doping, and chemical micropatterning. Nevertheless, the stability and controllability still need to be improved. In this study, we propose a feasible method that combines electrochemical bromination and photolithography to precisely tune the electron transport properties of single layer graphene (SLG). Through this …

Synergistic Effect Of Acylpyrazolone Integrated With Multiwalled Carbon Nanotubes On The Electrochemical Analysis Of Ascorbic Acid, Emi Norzehan Mohamad Mahbob, Mohamad Syahrizal Ahmad, Illyas Md Isa, Norhayati Hashim, Anwar Ul-Hamid, Mohamad Idris Saidin, Suyanta Suyanta, Sofian Ibrahim

Makara Journal of Science

Square wave voltammetry, cyclic voltammetry, chronocoulometry, and electrochemical impedance spectroscopy were employed to assess ascorbic acid’s electrochemical behavior in multiwalled carbon nanotubes (MWCNTs)/carbon paste electrode (CPE) modified by 1-phenyl-3-methyl-4-metafluorobenzoyl-5-pyrazolone (HPMmFBP). The ascorbic acid’s irreversible oxidation peak appeared at approximately 0.5 V. The shifting of the peak potential at the pH range of 6.0–8.4 showed the involvement of protons in the ascorbic acid oxidation. Moreover, the shifting of the peak potential with scan rate in the range of 0.07–0.4 V/s confirmed that the oxidation reaction was irreversible. Under optimized conditions, the oxidative peak current showed linear dependence on the ascorbic acid’s …

New Ways To Improve Dispersibility Of Nanotubes: Approaching From The Formation Of Silicon Nanoparticles By High Energy Reactive Ball Milling (Herbm) In Polar Solvents, Julie P. Vanegas, Yolanda V. Gutierrez, Joaquin Rivera, Juan García Jr.

Research Symposium

Background: This research aims to synthesize stable silicon nanoparticles using different molar ratios of N-Cyclohexyl-2-pyrrolidone (CHP) and Silicon to demonstrate if there is any significance towards the production of effective nanotubes. To determine this, the synthesized nanoparticles will be characterized by scanning electron microscopy (SEM), UV visible absorption spectroscopy, and photoluminescence spectroscopy (PL).

Methods: 50 Mg of silicon wafer are added with differing ratios of ligand (CHP), 5mL of water, and 3 steel iron balls into a ball milling vial. Vials are then placed into a ball milling apparatus for 7 cycles or 3.5 hours. Once the cycles are complete, …

Leveraging The Hmbc To Facilitate Metabolite Identification, Fatema Bhinderwala, Thao Vu, Thomas G. Smith, Julian Kosacki, Darrell D. Marshall, Yuhang Xu, Martha D. Morton, Robert Powers

Department of Chemistry: Faculty Publications

The accuracy and ease of metabolite assignments from a complex mixture are expected to be facilitated by employing a multi-spectral approach. The 2D ¹H-¹³C HSQC and 2D ¹H-¹H-TOCSY are the experiments commonly used for metabolite assignments. The 2D ¹H-¹³C HSQC-TOCSY and 2D ¹H-¹³C HMBC are routinely used by natural products chemists but have seen minimal usage in metabolomics despite the unique information, the nearly complete ¹H-¹H and ¹H-¹³C and spin systems provided by these experiments that may improve the accuracy and reliability …

Automated Workflow For Redox Potentials And Acidity Constants Calculations From Machine Learning Molecular Dynamics, Feng Wang, Jun Cheng

Journal of Electrochemistry

Redox potentials and acidity constants are key properties for evaluating the performance of energy materials. To achieve computational design of new generation of energy materials with higher performances, computing redox potentials and acidity constants with computational chemistry have attracted lots of attention. However, many works are done by using implicit solvation models, which is difficult to be applied to complex solvation environments due to hard parameterization. Recently, ab initio molecular dynamics (AIMD) has been applied to investigate real electrolytes with complex solvation. Furthermore, AIMD based free energy calculation methods have been established to calculate these physical chemical properties accurately. However, …

Measurements Of Rate Constant For Electrode Reactions, Lian-Huan Han, Jia-Yao Guo, Miao-Miao Cui

Journal of Electrochemistry

Standard electron-transfer rate constant is one of the intrinsic properties for an electrochemical reaction, which is significant in the study of electrode kinetics. It is a key criterion for one to clarify the mechanism and pathway of a specific electrochemical reaction, and to screening and design the electrocatalysts and battery materials. Herein, we will introduce the measuring methods of rate constant for electrode reactions, including polarization curve, rotating disk electrode, ultramicroelectrode, scanning electrochemical microscopy, electrochemical impedance spectroscopy, current step, potential step and cyclic voltammetry, etc., to provide a guide to investigate electrode kinetics for graduate students and researchers in the …

Tunable Magnetic Coupling In Graphene Nanoribbon Quantum Dots, Peter H. Jacobse, Mamun Sarker, Anshul Saxena, Brookhaven National Laboratory, Ziyi Wang, Emma Berger, Narayana R. Aluru, Alexander Sinitskii, Michael F. Crommie

Department of Chemistry: Faculty Publications

Carbon-based quantum dots (QDs) enable flexible manipulation of electronic behavior at the nanoscale, but controlling their magnetic properties requires atomically precise structural control. While magnetism is observed in organic molecules and graphene nanoribbons (GNRs), GNR precursors enabling bottom-up fabrication of QDs with various spin ground states have not yet been reported. Here the development of a new GNR precursor that results in magnetic QD structures embedded in semiconducting GNRs is reported. Inserting one such molecule into the GNR backbone and graphitizing it results in a QD region hosting one unpaired electron. QDs composed of two precursor molecules exhibit nonmagnetic, antiferromagnetic, …

Univariate Optimization Of Dispersive Liquid-Liquid Microextraction For Preconcentration Of Lead From Environmental Matrices, Samawah Region Prior To Quantification Using Flame Atomic Absorption Spectroscopy, Zaman Sahb Mehdi, Saher A. Ali Alshamkhawy

Al-Bahir

In this work, a procedure based on dispersive liquid₋liquid microextraction for lead (Pb) preconcentration and quantification in an environmental matrix by flame atomic absorption spectroscopy (FAAS) was applied. A case-study approach was chosen to obtain further in-depth information on the Pb levels. The green chemistry principles have been applied for the pretreatment and preparation of real samples by focusing on some features such as the volume of reagents/sample, employ of energy efficient equipment, and production of waste. A univariate strategy was utilized to achieve the optimum extraction conditions. 1750 µL of acetonitrile containing 100 µL of carbon tetrachloride, were rapid …

Papain-Catalyzed Synthesis Of Oligolysine In Low-Water Organic Reaction Media, Lakshmi Priya Ravikrishna, Krishnamurthi Tamilarasan, Vairamani Mariappanadar, Shubhender Kapila, Mathur Rajesh

Chemistry Faculty Research & Creative Works

Oligopeptides of l-lysine have the potential for applications in various scientific and technical areas. The number of residues in polycationic compounds such as oligolysine is also reported to have an effect on its biological properties. Hence, there is a necessity for developing efficient oligolysine synthesis methods where the oligopeptide dispersity can be tailored, along with optimum yield values. The ability of proteases to reverse their proteolytic activity to synthesize peptides has been reported in the literature. However, protease-catalyzed synthesis of oligopeptides of basic amino acids such as lysine in aqueous buffers is hindered by unfavorable thermodynamics. In this work, a …

Amperometric Bio-Sensing Of Lactate And Oxygen Concurrently With Local Field Potentials During Status Epilepticus, Eliana Fernandes, Ana Ledo, Greg A. Gerhardt, Rui M. Barbosa

Neurology Faculty Publications

Epilepsy is a prevalent neurological disorder with a complex pathogenesis and unpredictable nature, presenting limited treatment options in >30 % of affected individuals. Neurometabolic abnormalities have been observed in epilepsy patients, suggesting a disruption in the coupling between neural activity and energy metabolism in the brain. In this study, we employed amperometric biosensors based on a modified carbon fiber microelectrode platform to directly and continuously measure lactate and oxygen dynamics in the brain extracellular space. These biosensors demonstrated high sensitivity, selectivity, and rapid response time, enabling in vivo measurements with high temporal and spatial resolution. In vivo recordings in the …

Monodispersed Cu-Tcpp/Cu2O Hybrid Microspheres: A Superior Cascade Electrocatalyst Toward Co2 Reduction To C2 Products, Zi-Xuan Wan, Aidar Kuchkaev, Dmitry Yakhvarov, Xiong-Wu Kang

Journal of Electrochemistry

The electrochemical conversion of carbon dioxide (CO₂) into valuable chemicals is a feasible way to mitigate the negative impacts of overmuch CO₂ emissions. Porphyrin-based metal organic frameworks (MOFs) are expected to be used for selective and efficient electrochemical CO₂ reduction (ECR) with porous structure and ordered active sites. Herein, we report the synthesis of a monodispersed and spherical organic/inorganic hybrid Cu-TCPP@Cu₂O electrocatalyst composed of Cu-TCPP (TCPP=tetrakis (4-carboxyphenyl) porphyrin) and Cu₂O, where TCPP plays significant roles in regulating the morphology. In-situ formed Cu during ECR process in combination with Cu-TCPP (Cu-TCPP@Cu) can suppress …

Development Of Microfluidic Thermal Gel Electrophoresis For Biological Analysis, Mario Ambrocio Cornejo

Wayne State University Dissertations

ABSTRACTDEVELOPMENT OF MICROFLUIDIC THERMAL GEL ELECTROPHORESIS FOR BIOLOGICAL ANALYSIS by MARIO AMBROCIO CORNEJO May 2024 Advisor: Dr. Thomas H. Linz Major: Chemistry (Analytical Chemistry) Degree: Doctor of Philosophy The molecular biology that takes place within cells is vital to the over function of an organism. Healthy cellular function is crucial to a wide web of interconnected processes that need to be balanced and regulated. When these processes become abnormal, disease states are developed. The mapping of biological networks has led to the development of gene therapy and more accurate diagnostic tests. However, there are still vital biomolecules that due to …