Chemistry Commons^™

Inhibition Of The Self-Assembly Of Aβ And Of Tau By Polyphenols: Mechanistic Studies, Qiuchen Zheng, Micheal T. Kebede, Merc M. Kemeh, Saadman Islam, Bethany Lee, Stuart D. Bleck, Liliana A. Wurfl, Noel D. Lazo

Chemistry

The amyloid-β (Aβ) peptide and tau protein are thought to play key neuropathogenic roles in Alzheimer’s disease (AD). Both Aβ and tau self-assemble to form the two major pathological hallmarks of AD: amyloid plaques and neurofibrillary tangles, respectively. In this review, we show that naturally occurring polyphenols abundant in fruits, vegetables, red wine, and tea possess the ability to target pathways associated with the formation of assemblies of Aβ and tau. Polyphenols modulate the enzymatic processing of the amyloid-β precursor protein and inhibit toxic Aβ oligomerization by enhancing the clearance of Aβ42 monomer, modulating monomer–monomer interactions and remodeling oligomers to …

High Level Thermochemical And Spectroscopic Computations For Molecules Relevant To Combustion And The Atmosphere, Bradley K. Welch

Doctoral Dissertations

"Computational thermochemistry can be a complicated multistep process, but in recent years has become an equal partner with experiment. Many important molecules in combustion systems or in the atmosphere (such as short-lived radicals) are difficult to study experimentally. Predicting highly accurate thermochemistry is a key aspect in understanding these species. In this project, computational thermochemistry was developed into an automated streamlined procedure and then used to understand the methyl and ethyl peroxy families of radicals. This effort involved optimizing a standard workflow for computational thermochemistry. Computational thermochemistry generally requires numerous individual calculations whose cost and scalings vary widely. Conducting such …

The Benefit Of Precise Chemical Shift And Concentration Referencing In Nmr Applications, Ming Huang

Doctoral Dissertations

“In Nuclear Magnetic Resonance (NMR) spectroscopy, the chemical shift and intensity of NMR signals provide critical information about a sample's molecular structure, reaction conditions, and material properties. For the precise determination of structures and properties, it is critical to know sample or reaction conditions such as temperature, pH, concentration, or absolute amount of material. Chemical-shift and signal-intensity calibrations play a key role for extracting the maximum amount of information from NMR experiments. In this dissertation, internal and external reference standards are used to calibrate NMR spectra with respect to chemical shift and signal intensity. Sealed capillary tubes filled with specific …

Teaching With Technology: Using A Virtual Learning Community And Peer Mentoring To Create An Interdisciplinary Intervention, Rebecca Mazumdar, Nadia Benakli, Pamela Brown

Publications and Research

This paper describes the development and implementation of engaging and supportive experiences to promote student engagement, persistence and success at a commuter, open enrollment, public, minority serving institution. Project components included faculty development at the SENCER Summer Institute (SSI) 2016, attended by a team comprised of an academic administrator, full-time faculty from English and math, and part-time faculty in chemistry; creation of a virtual learning community of freshmen enrolled in chemistry, English, and math linked by the specific theme of the environmental impacts of deicing roads with salt and the overarching theme of the impacts of human activities on the …

Synthesis, Characterization And Antibacterial Properties Of Silver(I) N-(4-Pyridyl) Benzamide Complexes With Varying Conterions, Mauro J. Ruiz

Open Access Theses & Dissertations

Organic semiconductor materials composed of - stacking aromatic compounds have been under intense investigation for their potential uses in flexible electronics and other advanced technologies. Herein we report a new family of seven - stacking compounds of Silver(I) N-(4-pyridyl) Benzamide with varying counterions, namely [Ag(NPBA)2]X, where NPBA is N-(4-pyridyl) Benzamine, X = NO3- (1), ClO4- (2), CF3SO3- (3), PF6- (4), BF4- (5), CH3PhSO3- (6), and PhSO3- (7), which form extended - stacking networks in one-dimensional (1D), 2D and 3D directions in the crystalline solid-state via the phenyl moiety, with average inter-ring distances of 3.823 Å. Interestingly, the counterions that contain …

Minimalistic Supramolecular Proteoglycan Mimics By Co-Assembly Of Aromatic Peptide And Carbohydrate Amphiphiles, Alexandra Brito, Yousef M. Abul-Haija, Diana Soares De Costa, Ramon Novoa-Carballal, Rui L. Reis, Rein V. Ulijn, Ricardo A. Pires, Iva Pashkuleva

Advanced Science Research Center

We report the co-assembly of aromatic carbohydrate and dipeptide amphiphiles under physiological conditions as a strategy to generate minimalistic proteoglycan mimics. The resulting nanofibers present a structural, fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) core and a functional carbohydrate (Fmoc-glucosamine-6-sulfate or -phosphate) shell. The size, degree of bundling and mechanical properties of the assembled structures depend on the chemical nature of the carbohydrate amphiphile used. In cell culture medium, these nanofibers can further organize into supramolecular hydrogels. We demonstrate that, similar to proteoglycans, the assembled gels prolong the stability of growth factors and preserve the viability of cultured cells. Our results demonstrate that this approach …

Elq-331 As A Prototype For Extremely Durable Chemoprotection Against Malaria, Martin J. Smilkstein, Sovitj Pou, Alina Krollenbrock, Lisa A. Bleyle, Rozalia A. Dodean, Lisa Frueh, David J. Hinrichs, Multiple Additional Authors

Chemistry Faculty Publications and Presentations

The potential benefits of long-acting injectable chemoprotection (LAI-C) against malaria have been recently recognized, prompting a call for suitable candidate drugs to help meet this need. On the basis of its known pharmacodynamic and pharmacokinetic profiles after oral dosing, ELQ-331, a prodrug of the parasite mitochondrial electron transport inhibitor ELQ-300, was selected for study of pharmacokinetics and efficacy as LAI-C in mice.

Four trials were conducted in which mice were injected with a single intramuscular dose of ELQ-331 or other ELQ-300 prodrugs in sesame oil with 1.2% benzyl alcohol; the ELQ-300 content of the doses ranged from 2.5 to 30 …

Electronic Tuning Of Dimolybdenum Complexes Through Symmetry Manipulation Of Formamidinate Ligands In Their Second Coordination Sphere, Iván Alonso Cervantes Cervantes Martã­Nez

Open Access Theses & Dissertations

Alternative sustainable energy sources are required to decrease our dependence on carbon-based fuels. Small molecule activation is one of the most promising to fulfill global energy demand and maintain a sustainable world. Most of the industrial processes relevant for global energy supply and expenditure involves small molecules and metal catalysts. However, it is still required to gain fundamental insights on how these catalysts achieve such reactions. Dinuclear compounds, namely dimolybdenum complexes, may serve as a good experimental model to understand metal-metal cooperativity and its influence in catalysis.

In Chapter 2, three unsymmetric aryl formamidines were synthesized and characterized through 1H …

Low-Valent Synthons Of Titanium : Investigations On Structure-Reactivity Relationships, Rolando Aguilar

Open Access Theses & Dissertations

Strategies for the functionalization of abundant, small molecules into products with added value provide a powerful approach to address environmental sustainability issues. Dinitrogen (N2), and carbon oxides (CO, CO2), are examples of the ample, yet, underutilized atmospheric feedstock of nitrogen and carbon building blocks to produce a variety of chemicals. Although, potentially valuable, small molecules are inert under most conditions, and as such, their industrial activation often requires heterogeneous catalysts operated under high pressures (200 atm) and temperatures (450-600 ºC).

To this end, great efforts in synthetic inorganic chemistry have been devoted to the generation of well-defined and highly reactive …

Study Of Multielectron Redox Chemistry In Bimetallic Complexes And Metal-Free Macrocycles, Nancy Rodriguez Lopez

Open Access Theses & Dissertations

Multielectron redox chemistry is fundamental for the activation of small molecules (e.g. H2O, CO2, CO, N2). Although these processes are of great importance, they are not well understood. Unravelling the mechanisms of electron transfer and its principles is essential for the design and development of efficient catalysts. Our approach towards the understanding of multielectron redox chemistry includes theoretical study of mechanistic pathways in the hydrogen evolution reaction (HER) by metal-free porphyrinoids, the study of electronic communication in non-symmetric multimetallic two-state models (D–B–A) and the tuning of the electronic properties of bimetallic systems (Mo, and Au) by ligand control.

In Chapter …

Ibuprofen As A Probe Of Lipid Metabolism, Jose Antonio Rosales

Open Access Theses & Dissertations

The hypothesis that deracemization of racemic ibuprofen (IBU) occurs via the enolization of a Candida rugosa lipase (CRL)-ibuprofen ester (Scheme 1.6.2) was disproven by reacting racemic IBU under the conditions that were used to deracemize ibuprofen methyl ester (IME), namely pH 7.6. At pH 7.6, IME through IBU butyl esters were not formed in-situ and racemic IBU was not deracemized by reacting the corresponding primary alcohol with racemic IBU in the presence of CRL.

At pH 7.6, hexyl through dodecyl IBU esters were formed in-situ by reacting the corresponding primary alcohol with racemic IBU in the presence of CRL. The …

New Porous Semiconductor Nanocomposites As Dye-Sensitized Photocatalysts, Tahmina Akter

Open Access Theses & Dissertations

The wide band gap layered semiconductors potassium titanium niobium oxide (KTiNbO5) and potassium hexaniobate (K4Nb6O17) along with a metal co-catalyst can be been used to generate hydrogen fuel from water. However, ultraviolet light is required, which limits their utility in solar energy conversion. Modification of these types of semiconductors can sensitize them to visible light, providing a promising way to produce clean, renewable hydrogen (H2) fuel. Many photocatalysts suffer from poor H2 production efficiencies under visible light, due to inadequate and unstable sensitizers, resulting in photocatalysts that fail quickly.

In this research, several new high surface area dye sensitized nanocomposites …

Application Of Urinary Metabolites For Cancer Detection, Qin Gao

Open Access Theses & Dissertations

Prostate cancer (PCa) is the 3rd most common cause of male cancer mortality in the US. Early diagnosis and treatment of PCa will improve the quality of care and reduce mortality. The prostate specific antigen (PSA) is commonly used in the current PCa screening, but its limitation has resulted in an intense search for more reliable biomarkers. Studies showed that dogs could differentiate PCa patients from negative control by sniffing their urine. As the odor profiles are generated by volatile organic compounds (VOCs), the finding suggests that particular VOCs could be linked to PCa, PCa risk levels and other cancers. …

Synthesis Of Advanced Functional Nanomaterials For Sustainable Water Treatment Technologies, Md Tariqul Islam

Open Access Theses & Dissertations

Water is the most essential resource for the sustenance of life. Water is also necessary for agriculture, industry, household, and environmental conservation. However, due to large population growth and industrial expansion, access to clean water is becoming increasingly difficult around the world. Current water treatment technologies have not changed in over one hundred years and require a large infrastructure due to their low efficiencies and large-scale needs. In this context, the utilization of advanced functional nanomaterials and the adaptation of nanotechnology could potentially allow for miniaturizing water treatment and develop de-centralized solutions for rural areas. This Dissertation presents the design, …

Analysis Of Bodily Fluids Using Vibrational Spectroscopy: A Direct Comparison Of Raman Scattering And Infrared Absorption Techniques For The Case Of Glucose In Blood Serum, Drishya Prachalil, Clément Bruno, Franck Bonnier, Helen Blasco, Igor Chourpa, Matthew Baker, Jennifer Mcintyre, Hugh Byrne

Articles

Analysis of biomarkers present in the blood stream can potentially deliver crucial information on patient health and indicate the presence of numerous pathologies. The potential of vibrational spectroscopic analysis of human serum for diagnostic purposes has been widely investigated and, in recent times, infrared absorption spectroscopy, coupled with ultra-filtration and multivariate analysis techniques, has attracted increasing attention, both clinical and commercial. However, such methods commonly employ a drying step, which may hinder the clinical work flow and thus hamper their clinical deployment. As an alternative, this study explores the use of Raman spectroscopy, similarly coupled with ultra-filtration and multivariate analysis …

Rapid Analysis Of Magnesium In Infant Formula Powder Using Laser-Induced Breakdown Spectroscopy, Maria Markiewicz-Keszycka, Ming Zhao, Xavier Cama-Moncunill, Toufic El Arnaout, Dana Becker, Colm O'Donnell, P. J. Cullen, Carl Sullivan, Maria Piedad Casado-Gavalda

Articles

Laser-induced breakdown spectroscopy (LIBS) was investigated to determine magnesium (Mg) content in infant formula powder. To predict Mg content in the range established by the Codex Alimentarius, a partial least squares regression (PLSR) model was developed using a calibration data set (n = 30) based on full cross-validation and validated using an independent validation data set (n = 21). The prediction model performance was evaluated using the regression coefficients of determination (Rcv2 = 0.94 and Rp2 = 0.85) with the root mean square errors on cross-validation and prediction (RMSECV = 60 mg kg−1 and RMSEP = 80 mg kg−1). The …

Cross Faculty Collaboration In The Development Of An Integrated Mathematics And Science Initial Teacher Education Program, Sharon P. Fraser, Kim Beswick, Margaret Penson, Andrew Seen, Robert Whannell

Australian Journal of Teacher Education

This paper describes a collaborative project involving mathematicians, scientists and educators at an Australian university where an innovative initial teacher education (ITE) degree in mathematics/science was developed. The theoretical frameworks of identity theory and academic brokerage and their use in understanding the challenges associated with the early stages of collaborative projects is described. Data from reflections and interviews of the participants after involvement in the project from one to three years are presented to illustrate these challenges. The paper concludes with a description of the importance of the academic broker in overcoming identity challenges and facilitating cultural change for academics …

Molecular Dynamics Simulation Of Phenolic Compound Adsorption On Amine-Functionalized Carbon Nanotubes, Nutapong Tanatananon

Chulalongkorn University Theses and Dissertations (Chula ETD)

The interactions between green tea phenolic compounds, including (−)-epigallocatechin gallate (EGCG) and (−)-epigallocatechin (EGC), and various amine groups functionalized on carbon nanotube (CNT) were studied by all-atom molecular dynamics (MD) simulations. The amine functional groups: ethylenediamine (EDA), triethylenetetramine (TETA), and melamine (MA) were considered in this study. Simulated results showed that amine molecular structure grafted on CNT surface affected diffusion and adsorption of EGCG and EGC. The EDA-functionalized CNT (EDA/CNT) provided a strong adsorption affinity to EGCG and EGC with their bicyclic segments located within the EDA layer. It is because the functionalized-EDA structure was well-defined and given empty site …

Correlation Of Restitution Coefficient : Experiment And Computational Fluid Dynamics Simulation, Tarabordin Yurata

Chulalongkorn University Theses and Dissertations (Chula ETD)

The computational fluid dynamics with the discrete element method (CFD-DEM) is widely used to predict the hydrodynamics profile of the multiphase flow of fluid-solid or fluidization process. The coefficient of restitution (COR) is one of the most important parameters which is vital for CFD-DEM simulation. This parameter denotes the ratio of the relative velocity after the collision to the relative velocity before the collision. The appropriate value of the coefficient of restitution must receive attention to obtain the realistic collision and hydrodynamics profile. However, this parameter is still selected by trial and error in traditional CFD-DEM due to the lacking …

Density Functional Theory Study Of Aldol Condensation Between Furfural And 2-Butanone Over Magnesium Oxide, Wilasinee Heebnak

Chulalongkorn University Theses and Dissertations (Chula ETD)

Understanding of mechanistic and thermodynamic insights of the aldol condensation reaction is crucial to efficient catalytic conversion of biomass-derived oxygenates to fuel-range hydrocarbons. In this study, the aldol condensation of furfural and 2-butanone on magnesium oxide (MgO) catalyst was investigated using density functional theory (DFT) calculations. Energy profiles were computed for elementary steps, including Step 1: Formation of 2-butanone enolate, Step 2: Enolate addition at the carbonyl group of adsorbed furfural, and Step 3: Dehydration to form the condensation product. The DFT results showed that the enolization of 2-butanone was the rate-determining step. The methyl enolate can bind to MgO …

Metallophthalocyanine-Based Electrode For Sodium-Ion Batteries, Apinut Chongphanitkul

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this study, metallophthalocyanine-modified electrodes were fabricated and investigated for their electrochemical properties and energy storage performance. Six kinds of electrodes were prepared from indium tin oxide-coated glass (ITO-coated glass) substrates coated with titanium dioxide nanotube (TNT), poly(3,4-ethylenedioxythiophene) (PEDOT) and reduced graphene oxide (rGO) to improve conductivity of the substrates and surface area for the phthalocyanine-based materials. Target phthalocyanine monomers possess amino groups and Co(II) or Ni(II) central metals. On surface of each electrodes, films of the monomers were coated by a drop-casting technique, while those of their polymers were formed by electropolymerization. According to study on electrochemically active surface …

Molecular Dynamics Simulations Of M2 Channel In Phospholipid Bilayers With Different Thickness, Channarong Khrutto

Chulalongkorn University Theses and Dissertations (Chula ETD)

Two previous studies showed that M2 channel, a viral protein plays important role in replication of influenza virus, had different conformation after phospholipid bilayers thickness by using site-directed spin-label EPR spectroscopy (SDSL/EPR), one study, the M2 was spin-labeled on N-terminal amino acid residues, another one the M2 was spin-labeled on the C-terminal amino acid residues. Both studies supported each another. The more thickness phospholipid bilayer is the higher spin coupling value. It can be concluded that the conformation of M2 channel depends on phospholipid bilayer thickness. Data got from this technique is ambiguous, spin-spin coupling cannot be distinguishable, diagonal distance …

Interactions Of Pyrrolidinyl Peptide Nucleic Acid With Oligodeoxyguanosine And Biosensing Applications, Chayan Charoenpakdee

Chulalongkorn University Theses and Dissertations (Chula ETD)

Pyrrolidinyl peptide nucleic acid is a DNA mimic consisting of proline-2-aminocyclopentane carboxylic acid (acpcPNA) as a core structure. It binds to DNA to form a more stable hybrid while showing greater selectivity and affinity than the conventional DNA and PNA probes. In this study, we aim to develop novel DNA sensing systems based on the acpcPNA probe. In the first part, graphene oxide (GO) was used as an external quencher which could effectively quench the fluorescein-labeled PNA probe. A remarkable fluorescence restoration was achieved after the addition of a complementary DNA target. This acpcPNA-GO combination was successfully used to monitor …

Non-Hessian Method For Normal Coordinates Calculation, Chirayut Supunyabut

Chulalongkorn University Theses and Dissertations (Chula ETD)

Normal mode analysis (NMA) plays an essential role in chemistry for a very long time. It is both a key to understanding molecular motions, especially vibration motions, and to identifying characteristic peaks in infrared and Raman spectra. The traditional NMA requires the construction of a Hessian matrix and using harmonic approximation, which is almost impossible when large molecules and quantum mechanics are involved. Usually, NMA serves a complete set of normal coordinates that describes all possible motion modes of a molecule. This work presents a novel methodology to calculate normal coordinates that use only molecular geometries as input by considering …

Chemical Constituents Of Knema Angustifolia Stem And Biological Activities, Dung Le Thi Kim

Chulalongkorn University Theses and Dissertations (Chula ETD)

The medicinal plant Knema angustifolia has been used in Thai folk medicine for the treatment of various diseases, especially related to body tonic or blood tonic agent. Chemical data on this plant are scarce. A novel para-benzoquinone, angustiquinone (3), along with ten known compounds, rapanone (1), embelin (2), quercetin (4), kaempferol (5), bergenin (6), 11-O-acetyl bergenin (7), catechin (8), isovanillic acid (9), protocatechuic acid (10) and gallic acid (11) were isolated from the n-hexane and EtOAc extracts of the stems of K. angustifolia. Their structures were unambiguously elucidated using extensive 1D and 2D NMR analyses, high-resolution mass spectrometry along with …

Synthesis And Electropolymerization Of Phthalocyanine Derivatives For Electrochemical Reduction Of Carbon Dioxide, Jirapong Luangchaiyaporn

Chulalongkorn University Theses and Dissertations (Chula ETD)

This research describes synthesis and electrochemical polymerization of novel bithiophenyl-substituted phthalocyanines in order to get polymeric films that have electrocatalytic activities towards reduction of carbon dioxide (CO2). The target phthalocyanine monomers are synthesized by a two-step procedure including Suzuki reaction and cyclization of the resulting phthalonitrile. After that, electropolymerization of the target monomers on an indium tin oxide-coated glasses or carbon papers is performed by a cyclic voltammetry technique. The resulting polymer films are characterized by various spectroscopic methods. Catalytic performance towards the electrochemical reduction of CO2 of these polymers is investigated by the cyclic voltammetry and controlled potential electrolysis …

Synthesis And Development Of Nanocomposites Of Magnetic Nanoparticles-Silica-Mannan As Vaccine Adjuvants, Kamonlatth Rodponthukwaji

Chulalongkorn University Theses and Dissertations (Chula ETD)

Over the past years, vaccination has been considered as an effective treatment against a wide range of pathogens and diseases. Despite a promising outcome, the lack of strong immune response of some types of vaccines is still challenging. Therefore, targeting and activating dendritic cells (DCs) using nanomaterial-based vaccine adjuvant is of our interest. Herein, superparamagnetic iron oxide nanoparticles (SPIONs) have been exploited as directing agents to the targeted dendritic cells (DCs). In addition, mannan extracted from Saccharomyces cerevisiae was used as targeting molecules for targeting DCs. Nanocomposites of silica-magnetic nanoparticles-mannan (S-SPION-MN) were successfully fabricated. The synthesized particles were morphologically and …

Thread Based Wearable Electrochemical Sensor For Uric Acid Detection, Kanyapat Teekayupak

Chulalongkorn University Theses and Dissertations (Chula ETD)

Novel cotton thread-based electrochemical sensor was successfully fabricated for a non-invasive and non-enzymatic detection of uric acid (UA), a biomarker of gout disease. In this work, the working electrode was prepared by coating a carbon ink on the cotton thread to create the conductive property, followed by electrode modification using gold nanoparticles (AuNPs) to increase electrode surface area and conductivity. The morphologies of the modified electrode were characterized by scanning electron microscopy (SEM) with energy dispersive X-rays spectroscopy (EDX), confirming that AuNPs were modified on the electrode surface and the surface area of the modified electrode increased. The electrochemical characteristics …

Development Of Portable Electrochemical Sensors For Determination Of Heavy Metals, Nitrogen Oxides And Thiocyanate Ion, Kingkan Pungjunun

Chulalongkorn University Theses and Dissertations (Chula ETD)

This dissertation focused on the development of portable electrochemical sensors using the paper-based analytical device (ePAD) for the determination of the important compounds/biomarkers in various applications. Considering the target applications, this dissertation can be divided into three main parts including food safety application, environmental analysis and clinical application, respectively. In the first part, two sub-sections relating to the detection of heavy metals contaminated in food will be discussed. For the first sub-section, an ePAD coupled with a boron-doped diamond electrode was developed for the determination of total arsenic. The device was performed using the origami paper device for the preparation …

Synthesis Of Chalcone Derivatives As Ampk Activators, Duy Vu Nguyen

Chulalongkorn University Theses and Dissertations (Chula ETD)

Diabetes and diabetic nephropathy are two noticeable disorders in modern life. Chalcones are considered as a feasible candidate for these medication disorders due to the capability to activate AMPK relating to these two diseases. A series of chalcones with A-ring possessing 2'-hydroxy-, 3',4',5'-trimethoxyacetophenones or other types and B-ring decorated with mono-, di-, trisubstitution were accomplished by Claisen–Schmidt, etherification and hydrogenation reactions in almost moderate to high yield. 3-Methoxy group was found to be the best substituent for the activity in case of monosubstitution on B-ring. 3,4-Dimethoxy and 3,4-methylenedioxy groups on B-ring (63 and 65) enhanced the activity of disubstituted chalcones …