Physical Chemistry Commons^™

Developing Catalysts For The Hydrolysis Of Glycosidic Bonds In Oligosaccharides Using A Spectrophotometric Screening Assay, Susanna Striegler

Chemistry & Biochemistry Faculty Publications and Presentations

In a proof-of-concept study, a method for the empirical design of polyacrylate gel catalysts with the ability to cleave 1→4 α-glycosidic bonds in di- and trisaccharides was elaborated. The study included the synthesis of a 300-gel member library based on two different cross-linkers and 10 acrylate monomers, identification of monomodal gels by dynamic light scattering, and a 96-well plate spectrophotometric screening assay to monitor the hydrolysis of chromophore-free maltose into glucose units. The composition of the matrix of the most efficient catalysts in the library was found to enable CH−π, hydrophobic, and H-bond accepting interactions during the hydrolysis as typically …

Use Of Computational Methods To Determine The Relative Thermodynamic Stability Of Myricetin, Quercetin And 4-Methylesculetin For Use As Spin Traps, Cole Walker

Electronic Theses and Dissertations

The research conducted focused on the oxidative intermediates of antioxidants known as Myricetin, Quercetin, and 4-Methylesutin by calculating the reaction mechanism. During this research, computational quantum chemistry on selected parts for the 3 antioxidants previously mentioned were performed to find the most stable intermediate to act as a spin trap. The hypothesis is that the intermediates found can act as spin traps which will allow longer preservation of a free radical to be identified using Electron Paramagnetic Resonance (EPR) spectroscopy. This may be because the buildup of excess free radicals in a system leads them to cause damage down to …

Series Reports From Professor Wei’S Group Of Chongqing University: Advancements In Electrochemical Energy Conversions (1/4): Report 1: High-Performance Oxygen Reduction Catalysts For Fuel Cells, Fa-Dong Chen, Zhuo-Yang Xie, Meng-Ting Li, Si-Guo Chen, Wei Ding, Li Li, Jing Li, Zi-Dong Wei

Journal of Electrochemistry

Two major challenges, high cost and short lifespan, have been hindering the commercialization process of low-temperature fuel cells. Professor Wei’s group has been focusing on decreasing cathode Pt loadings without losses of activity and durability, and their research advances in this area over the past three decades are briefly reviewed herein. Regarding the Pt-based catalysts and the low Pt usage, they have firstly tried to clarify the degradation mechanism of Pt/C catalysts, and then demonstrated that the activity and stability could be improved by three strategies: regulating the nanostructures of the active sites, enhancing the effects of support materials, and …

Data-Driven Viewpoint For Developing Next-Generation Mg-Ion Solid-State Electrolytes, Fang-Ling Yang, Ryuhei Sato, Eric Jian-Feng Cheng, Kazuaki Kisu, Qian Wang, Xue Jia, Shin-Ichi Orimo, Hao Li

Journal of Electrochemistry

Magnesium (Mg) is a promising alternative to lithium (Li) in solid-state batteries due to its abundance and high theoretical volumetric capacity. However, the sluggish Mg-ion conduction in the lattice of solid-state electrolytes (SSEs) is one of the key challenges that hamper the development of Mg-ion solid-state batteries. Though various Mg-ion SSEs have been reported in recent years, key insights are hard to be derived from a single literature report. Besides, the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs. In this Viewpoints article, we analyze the structural characteristics of …

Professor Yong Yang, The Editorial Board Member Of Journal Of Electrochemistry, Is Elected As A Fellow Of The Electrochemical Society, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

Kai Wu, The Editorial Board Member Of Journal Of Electrochemistry And Chief Scientist Of Catl, Receives The National Science And Technology Progress Award, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

Sorbitol-Electrolyte-Additive Based Reversible Zinc Electrochemistry, Qiong Sun, Hai-Hui Du, Tian-Jiang Sun, Dian-Tao Li, Min Cheng, Jing Liang, Hai-Xia Li, Zhan-Liang Tao

Journal of Electrochemistry

The unstable zinc (Zn)/electrolyte interfaces formed by undesired dendrites and parasitic side reactions greatly hinder the development of aqueous zinc ion batteries. Herein, the hydroxy-rich sorbitol was used as an additive to reshape the solvation structure and modulate the interface chemistry. The strong interactions among sorbitol and both water molecules and Zn electrode can reduce the free water activity, optimize the solvation shell of water and Zn²⁺ ions, and regulate the formation of local water (H₂O)-poor environment on the surface of Zn electrode, which effectively inhibit the decomposition of water molecules, and thus, achieve the thermodynamically stable …

First Announcement Of 76th Annual Meeting Of The International Society Of Electrochemistry, International Society Of Electrochemistry (Ise)

Journal of Electrochemistry

No abstract provided.

Investigation Of Solvation Structures And Dynamics Of Li-Ion Battery Electrolytes And Amides In Water: An Infrared Spectroscopy, Electrochemical And Computational Study, Ernest O. Nachaki

LSU Doctoral Dissertations

The investigation of solvation structures and dynamics in lithium-ion battery electrolytes and amides in water has significant implications for both fundamental science and practical applications. Understanding the solvation dynamics of lithium electrolytes can lead to the development of safer and more efficient LIBs. The study of hydrogen bond dynamics of N-alkyl substituted amides has important implications for the development of thermos-responsive polymers used in biomedical applications. By understanding how N-alkyl substitutions affect the hydration structure and dynamics of amides, this research can inform the design of polymers with tailored properties for drug delivery, tissue engineering, and other medical applications. This …

Theoretical And Spectroscopic Insights Into Molybdenum- And Tungsten-Sulfur Bonding, Jesse Lepluart

Chemistry and Chemical Biology ETDs

Molybdenum and tungsten chemistry in biology is dominated by bonding interactions with sulfur and the other chalcogens. The highly-conserved structures of these enzymes’ active sites suggest an early evolution in the history of life, with molybdenum and/or tungsten enzymes likely expressed by the last universal common ancestor. Despite their active site similarities, molybdenum and tungsten enzymes catalyze a diverse array of reactions via equally diverse mechanisms. A deep understanding of the electronic structures of these enzyme active sites and their catalytic intermediates is key to understanding this remarkable chemistry.

The work presented here aims to deepen the understanding of molybdenum …

Fundamental Limits In Measuring The Anisotropic Rotational Diffusion Of Single Molecules, Weiyan Zhou, Tingting Wu, Matthew D. Lew

Electrical & Systems Engineering Publications and Presentations

Many biophysical techniques, such as single-molecule fluorescence correlation spectroscopy, Förster resonance energy transfer, and fluorescence anisotropy, measure the translation and rotation of biomolecules to quantify molecular processes at the nanoscale. These methods often simplify data analysis by assuming isotropic rotational diffusion, e.g., that molecules wobble within a circular cone. This simplification ignores the anisotropy present in many biological contexts that may cause molecules to exhibit different degrees of diffusion in different directions. Here, we loosen this assumption and establish a theoretical framework for describing and measuring anisotropic rotational diffusion using fluorescence imaging. We show that anisotropic wobble is directly quantified …

Tribocorrosion And Metal Release From Austenitic Stainless Steels 304 And 201 In Simulated Cassava Food Contact, Robert Addai, Temitope E. Olowoyo, Thalia E. Standish, Jeffrey Daniel Henderson, Ubong Eduok, Yolanda Hedberg

Chemistry Publications

Cassava is the third most significant calorie source in the tropics. Its processing has changed from traditional methods to stainless steel processing machines. This study investigated the influence of cassava on metal release from two common stainless steels, ASTM 304 and 201, with and without friction, and on tribocorrosion (multianalytically) of 304. Cassava was relatively corrosive and hindered repassivation of the surface oxide of stainless steel, but it also acted as a lubricant against mechanical friction. The combined action of friction and cassava caused a significant increase in iron, chromium, nickel, and manganese release from the stainless steels (30–35- fold …

Response To Replication Stress And Maintenance Of Genome Stability By Wrn, The Werner Syndrome Protein, David K. Orren, Amrita Machwe

Markey Cancer Center Faculty Publications

Werner syndrome (WS) is an autosomal recessive disease caused by loss of function of WRN. WS is a segmental progeroid disease and shows early onset or increased frequency of many characteristics of normal aging. WRN possesses helicase, annealing, strand exchange, and exonuclease activities and acts on a variety of DNA substrates, even complex replication and re- combination intermediates. Here, we review the genetics, biochemistry, and probably physiological functions of the WRN protein. Although its precise role is unclear, evidence suggests WRN plays a role in pathways that respond to replication stress and maintain genome stability particularly in telomeric regions.

Surface Structures And Properties Of High-Voltage Licoo2: Reviews And Prospects, Jian-Jun Fang, Yu-Hao Du, Zi-Jian Li, Wen-Guang Fan, Heng-Yu Ren, Hao-Cong Yi, Qing-He Zhao, Feng Pan

Journal of Electrochemistry

Nowadays, the development of high-voltage LiCoO₂ (lithium cobalt oxide, LCO) cathodes has attracted the widespread attention from both the academic and industry fields. Among the multiple concerns, researches on the surface issues would provide the most effective performance optimization pathway for the synthesis of high-voltage LCO. In this work, the issues of high-voltage LCO, including the phase transitions and crack formation, the oxygen redox related issues and side reactions, as well as the surface structure degradation, have been systematically reviewed. Then, we further clarify the surface modulations, and the interplay between the surface modulation and electrolyte tuning. Finally, we …

In Situ Diffuse Reflectance Spectroelectrochemistry Of Cathode Materials In Lithium-Ion Batteries, Lu-Lu Chen, Hao-Ran Li, Wei-Yi Liu, Wei Wang

Journal of Electrochemistry

Developing in situ spectroelectrochemistry methods, which can provide detailed information about species transformation during electrochemical reactions, is very important for studying electrode reaction mechanisms and improving battery performance. Studying real-time changes in the surface of electrode materials during normal operation can be an effective way to assess and optimize the practical performance of electrode materials, thus, in situ and in operando characterization techniques are particularly important. However, batteries are hard to be studied by in situ characterization measurements due to their hermetically sealed shells, and there is still much room for battery characterizations. In this work, a specially designed battery …

Molybdenum Disulfide And Carbon Nanotubes Composite Electrode For Electrochemical Conversion Of Salinity Gradient Energy, Jia-Jun Li, Wei-Bin Zhang, Xin-Yu Liu, Jing-Lei Yang, Yi Yin, Ze-Qin Yang, Xue-Jing Ma

Journal of Electrochemistry

The ocean accounts for 97% of the total water resources on earth, covering over 70% of the map's surface area. With the continuous consumption of non-renewable energy sources such as fossil fuels and the rapid development of renewable energy, humans are increasingly paying attention to the utilization of ocean resources. Ocean energy includes tidal energy, wave energy, temperature difference energy, and salinity gradient energy. Salinity gradient energy is the energy generated by the interaction of seawater and fresh water, which is the ocean energy existing in the form of chemical energy. This energy is mostly generated in estuaries. The osmotic …

Thermal Effects On The Voc-Sensitive Polydimethylsiloxane Holographic Gratings, Aleksandra Hernik, Faolan Radford Mcgovern, Patrick Iftime, Izabela Naydenova

Conference Papers

The imperative for monitoring volatile organic compounds (VOCs) emerges from their harmful impact on human health when inhaled excessively over a long term. Polydimethylsiloxane (PDMS), valued for its transparency and excellent flexibility, has already been demonstrated as a promising biocompatible and cost-effective transducer for optical VOCs sensing. Moreover, it facilitates further functionalisation with adsorbing materials to enhance sensitivity and selectivity for specific VOCs detection. We fabricated and examined PDMS-based surface diffraction gratings after exposure to selected VOCs, demonstrating different response for polar and non-polar molecules. Investigated gratings were prepared by replicating sinusoidal surface relief structures inscribed in acrylamide photopolymer using …

Predicting Ph At In-Situ Temperature For Aquatic Environments, Sarah E. Bartoloni

USF Tampa Graduate Theses and Dissertations

pH is typically measured at a constant temperature and, as needed, converted to in-situ temperature using a system of thermodynamic equations. Using this equilibrium approach, adjustment of pH to in situ conditions requires two measured CO2 system parameters (pH, total alkalinity, dissolved inorganic carbon, or CO2 fugacity). Currently, when pH is the only measured CO2 system parameter, linear models are used to adjust the pH to in-situ temperature. Although many studies have attempted to optimize CO2 equilibrium constants (K1 and K2) for the CO2 system over a range of conditions, very little prior work has experimentally examined which CO2 system …

Assigning The Ch Stretch Overtone Spectrum Of Benzene And Naphthalene With Extension To Anthracene And Tetracene Using 2- And 3-Quanta Anharmonic Quantum Chemical Computations, Vincent J. Esposito, Ryan C. Fortenberry, Christiaan Boersma, Louis J. Allamandola

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The CH stretch overtone region (5750–6300 cm⁻¹) of benzene and naphthalene is assigned herein using anharmonic quantum chemical computations, and the trend of how this extends to larger polycyclic aromatic hydrocarbons (PAHs) is established. The assignment of all experimental bands to specific vibrational states is performed for the first time. Resonance polyads and the inclusion of 3-quanta vibrational states are both needed to compute accurate vibrational frequencies with the proper density-of-states to match the experimental band shape. Hundreds of 3-quanta states produce the observed band structure in naphthalene, anthracene, and tetracene, and this number is expected to increase …

Dft Based Modeling Of The Heavy Atom Effect In Triplet Photosensitizers: From Fundamental Mechanics To Rational Design, Bret Andrew Steinkamp

Dissertations and Theses

Photochemistry is the study of how light interacts with molecules and includes both the absorption and release of light. This document focuses on triplet photosensitizers -- molecules that utilize the excited triplet state -- for a variety of applications including photodynamic therapy and photocatalysis. There are many factors that influence the design of triplet photosensitizers; in this work, we have developed and used a methodology for the rational design of triplet photosensitizers based on an approximation of the heavy atom effect (HAE) from density functional theory calculations and the experimentally measured singlet oxygen quantum yield (Ф_Δ).

As excited …

Simulation Of Linear And Cyclic Alkanes With Second-Order Møller–Plesset Perturbation Theory Through Adaptive Force Matching, Alexei Nikitin, Feng Wang

Chemistry & Biochemistry Faculty Publications and Presentations

Predicting ensemble properties, such as density and heat of vaporization, of small hydrocarbons is challenging due to the dispersion-dominated weak interactions between these molecules. With the adaptive force matching (AFM) method, the bonded and short-range nonbonded interactions are fitted to second-order Møller–Plesset perturbation theory (MP2) references computed with the def2-TZVP basis set. The dispersion is modeled using symmetry adapted perturbation theory (SAPT) at MP4 accuracy using the def2-TZVPD basis set. A new charge matrix decomposition technique is described to obtain partial charges in AFM. Although the models developed do not have any empirical parameters, several properties of the resulting models …

2-Tertbutylfuran At 550 And 700 K: A Multiplexed Photoionization Mass Spectrometric Investigation And Determination Of Cross Sections Of A Carbon- Bromine Bond And Various Brominated Organic Compounds, Ameyali Tapia

Master's Theses

This thesis presents the combustion study of 2-tertbutylfuran (2-TBF) in reaction with atomic oxygen (O(3P)). Data was collected at the Advanced Light Source (ALS) of the Lawrence Berkeley National Lab, using tunable vacuum ultraviolet radiation coupled with a multiplexed mass spectrometer to acquire the data. These data were taken at low pressures of 7 and 8 torr at temperatures of 550 K and 700 K, respectively. Primary products of the system were identified and characterized, while reaction pathways of the products are currently being studied to ensure thermodynamic feasibility. Branching fractions of the system were also calculated, to view the …

Recent Advance In Electrochemical Dehalogenative Deuteration, Peng-Fei Li, Guang-Sheng Kou, Li-Ping Qi, You-Ai Qiu

Journal of Electrochemistry

In recent years, the incorporation of deuterium atoms into organic compounds has emerged as a vital focus in the development of pharmaceutical molecules. This trend is driven by the increasing recognition of the significance of compounds containing deuterium atoms across various domains, including materials and biopharmaceuticals, where they have found widespread applications in mechanistic studies within the realms of chemistry and biology. Meanwhile, organic electrochemistry, as a relatively environmentally friendly catalytic mode with broad adaptability to redox reactions, has emerged as a crucial alternative to traditional halogen-deuterium exchange in the context of the reduction deuteration of halides. This approach circumvents …

Comparison Of Ligands In Palladium-Catalyzed Electrochemical Allyl 4-Pyridinylation, Wei-Jie Ding, Chun-Hui Yang, Zhong-Tao Feng, Shi-Rong Lu, Xu Cheng

Journal of Electrochemistry

4-CN-pyridine is a widely applied 4-pyridinylation reagent for diverse transformations. Conventionally, the reaction proceeds via an open-shell radical cross-coupling pathway. Following our previous study, in this work, we report the Pd-catalyzed allyl 4-pyrinylation reaction under electrochemical conditions. The reaction proceeds via radical-polar crossover pathway in which the role of phosphine ligand in reactivity and selectivity was extensively investigated.

Nickel-Catalyzed Α-Arylation Of Α-Cyanoacetates Enabled By Electrochemistry, Zi-Meng Li, Zhang-Jian Li, Anat Milo, Ping Fang, Tian-Sheng Mei

Journal of Electrochemistry

β-Amino acids have a wide range of applications in the field of pharmaceuticals. Utilizing a combination strategy of nickel catalysis and paired electrolysis, a catalytic α-arylation protocol of carbonyl compounds has been developed. This protocol affords various a-aryl-a-cyanoacetates, which can be reduced to high-value-added α-aryl-β-amino acids. The cross-coupling reaction of electron-deficient aryl bromides with a-cyanoacetates achieves the expected products with good yields and functional group compatibility under mild conditions. Excessive electron-richness in initial aryl bromides facilitates the self-coupling of desired products. DFT calculations confirm that the presence of electron-rich aryl substitutions decreases the reduction potentials of the product anions, making …

The Lewis Acidity Of Imidazole-Derived Diaryliodonium Zwitterions, Cyrus Rose

University Honors Theses

Diaryliodonium salts can be used as effective aryl-transfer agents in reactions to form novel molecules with diverse applications including pharmaceuticals and agrochemicals without using harsh reaction conditions and transition metal reagents. In recent years, interest in the applications of the Lewis acidity of iodonium ion catalysts has increased. Despite this, the quantification of the Lewis acidities of diaryliodonium salts are scarce. Even rarer, there has not been much study into the Lewis acidities of zwitterionic diaryliodonium salts. For zwitterions, there is no counter anion that would come into consideration in regard to its Lewis acidity. To expand the understanding of …

The Investigation Of The Reaction Of 2,3-Dimethylfuran With O(³P) And The Estimate Of The Photoionization Cross Section Of C-Cl And Absolute Photoionization Cross Sections Of Chlorinated Organic Compounds, Yilan Lori Chen

Master's Theses

The work presented in this thesis focuses on gas-phase reactions, which are fundamental for reducing greenhouse gas emissions and mitigating climate change. The experiments are performed at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory, where there is a time-of-flight mass spectrometer coupled with tunable synchrotron radiation at Beamline 9.0.2 to collect high-quality data.

Chapter 1 details the background and purpose of each project, along with an overview of the origins of synchrotron radiation and time-of-flight mass spectrometry. The adaptation of biofuels is a way to minimize carbon emission and air pollutants, so research surrounding the reaction dynamics …

Theoretical Spectroscopic Predictions Of Electronically Excited States, Noah R. Garrett

Honors Theses

The quest for faster computation of anharmonic vibrational frequencies of both ground and excited electronic states has led to combining coupled cluster theory harmonic force constants with density functional theory (DFT) cubic and quartic force constants for defining a quartic force field (QFF) utilized in conjunction with vibrational perturbation theory at second order (VPT2). This work shows that explicitly correlated coupled cluster theory at the singles, doubles, and perturbative triples level [CCSD(T)-F12] provides accurate anharmonic vibrational frequencies and rotational constants when conjoined with any of B3LYP, CAM-B3LYP, BHandHLYP, PBE0, and ωB97XD for roughly one-quarter of the computational time of the …

Cn Stretches Around 4.4 Microns Dominate The Ir Absorption Spectra Of Cyanopolycyclic Aromatic Hydrocarbons, Vincent J. Esposito, Ryan C. Fortenberry, Christiaan Boersma, Alexandros Maragkoudakis, Louis J. Allamandola

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Anharmonic quantum chemical computations reveal a strong, narrow (width = 0.075 μm) band in the 4.3–4.5 μm region of the absorption spectra of the cyano-substituted polycyclic aromatic hydrocarbons (CN-PAHs) cyanonaphthalene, cyanoanthracene, c yanophenanthrene, and c yanopyrene. This narro w windo w with intense IR lines implies that CN-PAHs of various shapes and sizes offer little variation in both wavelength and intensity in this region. Subsequently, this band can be used as a tracer for CN-PAHs. The distinct features making up the band are assigned to mixed vibrational states consisting of the CN stretch fundamental and various combination bands, including in-plane …

Investigating The Impact Of Secondary Activation Time On The Adsorption Properties Of Activated Biochar For Arsenic Removal From Wastewater, Achyuth Bharadwaj Rayarao

Graduate Theses and Dissertations (2019 - present)

Biochar, a naturally occurring and renewable carbon material, becomes porous through activation. Activated biochar is an ideal candidate for use as an adsorbent. The objective of this study is to investigate whether activated biochar derived from Colorado soft pine serves as a better adsorbent and demonstrates enhanced adsorption capabilities after undergoing secondary physical activation at various activation times. The effect of secondary action time on physical adsorption properties drawn from the analysis of isotherm plots, surface areas and pore size patterns were examined by using a physisorption analyzer. Chemical structures were identified using both ultimate and proximate analyses, while porosity …