Biochemistry, Biophysics, and Structural Biology Commons^™

Sharing The Salt Bowl: Counterion Identity Drives N-Alkyl Resorcinarene Affinity For Pyrophosphate In Water, Kwaku Twum, Seyed Iraj Sadraei, Jordan Feder, S. Maryamdokht Taimoory, Kari Rissanen, John F. Trant, Ngong Kodiah Beyeh

Chemistry and Biochemistry Publications

N-Alkyl ammonium resorcinarene chloride receptors, NARX4, have been shown to act as high-sensitivity detectors of pyrophosphate (PPi), a biomarker of disease, in aqueous media through the chloride-to-PPi exchange [NAR(Cl)4 to NARPPi]. The nature of the anion of the macrocyclic NARX4 (X = Cl−, Br−, triflate OTf−) receptor greatly influences the PPi-affinity in aqueous media. The binding affinity for [NAR (Cl)4] is 3.61 × 105 M−1, while the NAR (Br)4 and NAR (OTf)4 show stronger binding of 5.30 × 105 M−1, and 6.10 × 105 M−1, respectively. The effects of upper rim ammonium cation, –N+H2R substituents (R = 3-hydroxypropyl, cyclohexyl, …

High-Resolution Cryo-Electron Microscopy Structure Of Photosystem Ii From The Mesophilic Cyanobacterium, Synechocystis Sp. Pcc 6803, Christopher J. Gisriel, Jimin Wang, Jinchan Liu, David A. Flesher, Krystle M. Reiss, Hao-Li Huang, Ke R. Yang, William H. Armstrong, M. R. Gunner, Victor S. Batista, Richard J. Debus, Gary W. Brudvig

Publications and Research

Photosystem II (PSII) enables global-scale, light-driven water oxidation. Genetic manipulation of PSII from the mesophilic cyanobacterium Synechocystis sp. PCC 6803 has provided insights into the mechanism of water oxidation; however, the lack of a highresolution structure of oxygen-evolving PSII from this organism has limited the interpretation of biophysical data to models based on structures of thermophilic cyanobacterial PSII. Here, we report the cryo-electron microscopy structure of PSII from Synechocystis sp. PCC 6803 at 1.93-Å resolution. A number of differences are observed relative to thermophilic PSII structures, including the following: the extrinsic subunit PsbQ is maintained, the C terminus of the …

Reaction Of Alkynyl- And Alkenyltrifluoroborates With Propargyldicobalt Cations: Alkynylation, Alkenylation, And Cyclopropanation Product Pathways, Brent St Onge, S. Maryamdokht Taimoory, Jeffrey Battersby, John F. Trant, James R. Green

Chemistry and Biochemistry Publications

The Lewis acid-mediated Nicholas reactions of propargyl acetate–Co2(CO)6 complexes with a series of potassium alkynyltrifluoroborates and potassium alkenyltrifluoroborates are described. Alkynyltrifluoroborates directly alkynylate the intermediate propargyldicobalt cations. In contrast, alkenyltrifluoroborates proceed through one of the three modes of dominant reactivity: C-2-substituted alkenyltrifluorobrates directly alkenylate, predominantly with the retention of stereochemistry. C-1-substituted alkenyltrifluoroborates alkenylate at C-2. Potassium vinyltrifluoroborate incorporates a cyclopropane at the site propargyl to alkynedicobalt. Computational analysis of these systems explains the differential modes of reactivity of alkenyltrifluoroborates and outlines the probable mechanisms for the formation of each product.

Protocol For Fabricating Electroless Nickel Immersion Gold Strain Sensors On Nitrile Butadiene Rubber Gloves For Wearable Electronics, Sara S. Mechael, Yunyun Wu, Yiting Chen, Tricia Breen Carmichael

Chemistry and Biochemistry Publications

This protocol describes the fabrication of patterned conductive gold films on nitrile butadiene rubber (NBR) gloves for wearable strain sensors using electroless nickel immersion gold (ENIG) plating, a solution-based metallization technique. The resulting NBR/ENIG films are strain sensitive; resistance measurements of a patterned sensing array can be used to map human hand motions. This protocol also describes challenges related to the ENIG process and troubleshooting steps to achieve conformal gold films for strain sensing over a large working range. For complete details on the use and execution of this protocol, please refer to Mechael et al. (2021).

Single-Variable Porous Nanomaterial Series From Polymer Structure-Directing Agents, Morgan Stefik

Faculty Publications

Block polymer structure-directing agents (SDA) enable the production of porous nanoscale materials. Most strategies rely upon polymer equilibration where diverse morphologies are realized in porous functional materials. This review details how solvent selectivity determines the polymer SDA behaviors, spanning from bulk-type to solution-type. Equilibrating behavior of either type, however, obscures nanostructure cause-and-effect since the resulting sample series convolve multiple spatial variations. Solution-type SDA behaviors include both dynamic and persistent micelles. Persistent micelle templates (PMT) use high solvent selectivity for kinetic entrapment. PMTs enable independent wall thickness control with demonstrated 2 Å precision alterations. Unimodal PMT pore size distributions have spanned …

Synergistic Broad-Spectrum Antibacterial Activity Of Hypoxis Hemerocallidea-Derived Silver Nanoparticles And Streptomycin Against Respiratory Pathobionts, Oluwole S. Aremu, T. Qwebani-Ogunleye, Lebogang Katata-Seru, Zimbili Mkhize, John F. Trant

Chemistry and Biochemistry Publications

Respiratory tract infections arise due to the introduction of microbes into the airway, disrupting the normal, healthy, complex interdependent microbiome. The selective disruption of this community can be either beneficial or dangerous. Nanoparticles are a potential tool for modifying this population. Coated silver nanoparticles (AgNPs) were synthesized using ethanolic extracts of Hypoxis hemerocallidea (EEHH), a Southern African plant used extensively in traditional medicine and the source of many bioactive secondary metabolites. The room temperature reaction between silver nitrate and EEHH forms largely spherical AgNPs with an average diameter of 6–20 nm. These nanoparticles show similar levels of antibacterial activity as …

New Isolate From Salvinia Molesta With Antioxidant And Urease Inhibitory Activity, Nadra Naheed, Saima Maher, Farooq Saleem, Ajmal Khan, Abdul Wadood, Saima Rasheed, M. Iqbal Choudhary, Matheus Froeyen, Iskandar Abdullah, Muhammad Usman Mirza, John F. Trant, Sarfraz Ahmad

Chemistry and Biochemistry Publications

Urease plays a significant role in the pathogenesis of urolithiasis pyelonephritis, urinary catheter encrustation, hepatic coma, hepatic encephalopathy, and peptic acid duodenal ulcers. Salvinia molesta was explored to identify new bioactive compounds with particular emphasis on urease inhibitors. The aqueous methanol extract was fractionated using solvents of increasing polarity. A series of column chromatography and later HPLC were performed on butanol extract. The structures of the resulting pure compounds were resolved using NMR (1D and 2D), infrared, and mass spectroscopy. The novel isolate was evaluated for antioxidant activity (using DPPH, superoxide anion radical scavenging, oxidative burst, and Fe+2 chelation assays), …

Evaluation Of The Trunarc Handheld Narcotics Analyzer As A Pre-Analysis Screening Device For The Orange County Crime Lab, Sarah Yang, D. Bauer, C. Woltz, S. Soto, Michael Ibba

Student Scholar Symposium Abstracts and Posters

Forensic analysis of suspected narcotics is often dangerous as the substances’ composition is unknown. Many techniques for drug identification require handling of the substance outside of its packaging, which can expose the analyst to potentially harmful chemicals. The TruNarc Handheld Narcotics Analyzer is a portable Raman spectroscopy device that is non-destructive of evidence and can be used to screen drugs through simple packaging to minimize the risk of exposure. The Orange County Crime Lab (OCCL) is testing the limits of this device to determine if it can be used to screen new evidence within the Seized Drugs Lab. The OCCL …

From Fat To Bilayers: Understanding Where And How Vitamin E Works, Jeffrey Atkinson, Drew Marquardt, Mitchell Dipasquale, Thad Harroun

Chemistry and Biochemistry Publications

Vitamin E was one of the last fat-soluble vitamins to be discovered. We provide here an historical review of the discovery and the increasingly more detailed understanding of the role of α-tocopherol both as an antioxidant and as a structural component of phospholipid bilayer membranes. Despite the detailed descriptions now available of the orientation, location, and dynamics of α-tocopherol in lipid bilayers, there are still gaps in our knowledge of the effect of α-tocopherol and its potential receptors than control gene transcription.

Aptamer-Based Voltammetric Biosensing For The Detection Of Codeine And Fentanyl In Sweat And Saliva, Rosa Lashantez Cromartie

FIU Electronic Theses and Dissertations

Despite the many governmental and medicinal restrictions created to combat the opioid epidemic in the United States, opioid abuse and overdose rates continue to rise. The development of an aptamer-based voltammetric sensor and biosensor is described in this dissertation. The aim was to develop a low-cost, sensitive, and specific aptamer-based sensor for on-site, label-free determination of codeine and fentanyl in biological fluids. To do this, the surfaces of screen-printed carbon electrodes (SPCE) were modified with gold nanoparticles (AuNPs), followed by the addition of single-stranded DNA aptamers. These were covalently bound to the electrode surface. Operations of the sensors were collected …

Efficient And Reproducible Synthesis Of An Fmoc-Protected Tn Antigen, Sabrina M. Piazza, Michael R. Reynolds, Jonathan Chiaramonte, Peihan Xu, Fabiola A. Chapa-Villarreal, John F. Trant

Chemistry and Biochemistry Publications

This concise total synthesis of the Thomsen-Nouveau (Tn) glycoconjugate was accomplished using a palladium-catalyzed coupling between the glycosyl donor and Fmoc-protected serine acceptor. This is, to the best of our knowledge, the shortest synthesis reported from galactose for preparing this essential building block for large-scale solid phase peptide synthesis.

A Calorimetric, Volumetric And Combined Sans And Saxs Study Of Hybrid Siloxane Phosphocholine Bilayers, Mark B. Frampton, Doruntina Yakoub, John Katsaras, Paul M. Zelisko, Drew Marquardt

Chemistry and Biochemistry Publications

Siloxanes are molecules used extensively in commercial, industrial, and biomedical applications. The inclusion of short siloxane chains into phospholipids results in interesting physical properties, including the ability to form low polydispersity unilamellar vesicles. As such, hybrid siloxane phosphocholines (SiPCs) have been examined as a potential platform for the delivery of therapeutic agents. Using small angle X-ray and neutron scattering, vibrating tube densitometry, and differential scanning calorimetry, we studied four hybrid SiPCs bilayers. Lipid volume measurements for the different SiPCs compared well with those previously determined for polyunsaturated PCs. Furthermore, the different SiPC's membrane thicknesses increased monotonically with temperature and, for …

Computational Simulation Of The Lung Doses Of Air-Borne Fine And Ultrafine Particles Inhaled By Humans At Industrial Workplaces, Mohammed Ali

Technology Faculty Publications and Presentations

This study correlates computational predictions with in-vivo experimental results of inhaled fine and ultrafine particulate matters (PMs) transport, dissemination, and deposition in the human respiratory airways. Epidemiological studies suggest that workplace exposure of anthropogenic pollutant PMs as a risk factor for increased susceptibility to acute broncho-pulmonary infections. However, investigations on detailed human inhalation and PM transport processes are restrictive from time, cost, and ethical perspectives. To overcome this problem, computational simulation of particle deposition based on the Multiple Path Particle Dosimetry (MPPD) model was employed. Here, the physical, mechanical, and electrical properties of PMs of carbon black and nanoparticles from …

Bisindolylmaleimide Ix: A Novel Anti-Sars-Cov2 Agent Targeting Viral Main Protease 3clpro Demonstrated By Virtual Screening Pipeline And In-Vitro Validation Assays, Yash Gupta, Dawid Maciorowski, Samantha E. Zak, Krysten A. Jones, Rahul S. Kathayat, Saara-Anne Azizi, Raman Mathur, Catherine M. Pearce, David J. Ilc, Hamza Husein, Andrew S. Herbert, Ajay Bharti, Brijesh Rathi, Ravi Durvasula, Daniel P. Becker, Bryan C. Dickinson, John M. Dye, Prakasha Kempaiah

Chemistry: Faculty Publications and Other Works

SARS-CoV-2, the virus that causes COVID-19 consists of several enzymes with essential functions within its proteome. Here, we focused on repurposing approved and investigational drugs/compounds. We targeted seven proteins with enzymatic activities known to be essential at different stages of the viral cycle including PLpro, 3CLpro, RdRP, Helicase, ExoN, NendoU, and 2′-O-MT. For virtual screening, energy minimization of a crystal structure of the modeled protein was carried out using the Protein Preparation Wizard (Schrodinger LLC 2020-1). Following active site selection based on data mining and COACH predictions, we performed a high-throughput virtual screen of drugs and investigational molecules (n = …

Accident Experiences And Reporting Practices In Canadian Chemistry And Biochemistry Labs: A Pilot Investigation, Dana Ménard, John F. Trant

Chemistry and Biochemistry Publications

Accidents in chemistry and biochemistry laboratories are a regular occurrence and have been associated with injuries, property damage, and deaths. However, despite a high prevalence rate of accident involvement reported in previous investigations of academic lab personnel (approximately 30%), little is known about the context in which academic lab accidents occur. Previous findings also suggest a high degree of accident underreporting (25–40%), but again, little is known about this phenomenon. Pilot data was gathered from a convenience sample of 104 students and postdoctoral fellows in chemistry-related fields through an online survey. Results showed a high level of accident involvement (56.7%); …

Fabrication Of An Autonomously Self-Healing Flexible Thin-Film Capacitor By Slot-Die Coating, Susanna Vu, Gnanesh Nagesh, Nastaran Yousefi, John F. Trant, David S.K. Ting, M. Jalal Ahamed, Simon Rondeau-Gagné

Chemistry and Biochemistry Publications

Flexible pressure sensors with self-healing abilities for wearable electronics are being developed, but generally either lack autonomous self-healing properties or require sophisticated material processing methods. To address this challenge, we developed flexible, low-cost and autonomously self-healing capacitive sensors using a crosslinked poly(dimethylsiloxane) through metal-ligand interactions processed into thin films via slot-die coating. These films have excellent self-healing properties, approximately 1.34 × 105 μm3 per hour at room temperature and 2.87 × 105 μm3 per hour at body temperature (37 °C). Similarly, no significant change in capacitance under bending strain was observed on these flexible thin-films when assembled on poly(ethyleneterephthalate) (PET) …

A Study Of The Mammalian High Mobility Group Protein At-Hook 2 (Hmga2) And Its Interactions With Dna, Linjia Su

FIU Electronic Theses and Dissertations

The mammalian high-mobility-group protein AT-hook 2 (HMGA2) is a small DNA-binding protein and consists of three positively charged “AT-hooks” and a negatively charged C-terminal motif. It is a multifunctional nuclear protein linked to obesity, human height, stem cell youth, human intelligence, and tumorigenesis. Previous results showed that HMGA2 is a potential therapeutic target of anticancer and anti‐obesity drugs through inhibiting its DNA‐binding activities. Here a miniaturized, automated AlphaScreen ultra‐high‐throughput screening assay is developed to identify inhibitors targeting HMGA2‐DNA interactions. After screening the LOPAC1280 library, several compounds are identified that strongly inhibit HMGA2‐DNA interactions including suramin, a negatively charged antiparasitic drug. …

Fe-Catalyzed Sulfide Oxidation In Hydrothermal Plumes Is A Source Of Reactive Oxygen Species To The Ocean, Timothy J. Shaw, George W. Luther Iii, Richard Rosas, Véronique E. Oldham, Nicole R. Coffey, John L. Ferry, Dewamunnage M. C. Dias, Mustafa Yücel, Aubin Thibault De Chanvalon

Faculty Publications

Historically, the production of reactive oxygen species (ROS) in the ocean has been attributed to photochemical and biochemical reactions. However, hydrothermal vents emit globally significant inventories of reduced Fe and S species that should react rapidly with oxygen in bottom water and serve as a heretofore unmeasured source of ROS. Here, we show that the Fe-catalyzed oxidation of reduced sulfur species in hydrothermal vent plumes in the deep oceans supported the abiotic formation of ROS at concentrations 20 to 100 times higher than the average for photoproduced ROS in surface waters. ROS (measured as hydrogen peroxide) were determined in hydrothermal …

Oxidation Alters The Architecture Of The Phenylalanyl-Trna Synthetase Editing Domain To Confer Hyperaccuracy, Pooja Srinivas, Rebecca E. Steiner, Ian J. Pavelich, Ricardo Guerrera-Ferreira, Puneet Juneja, Michael Ibba, Christine M. Dunham

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

High fidelity during protein synthesis is accomplished by aminoacyl-tRNA synthetases (aaRSs). These enzymes ligate an amino acid to a cognate tRNA and have proofreading and editing capabilities that ensure high fidelity. Phenylalanyl-tRNA synthetase (PheRS) preferentially ligates a phenylalanine to a tRNA^Phe over the chemically similar tyrosine, which differs from phenylalanine by a single hydroxyl group. In bacteria that undergo exposure to oxidative stress such as Salmonella enterica serovar Typhimurium, tyrosine isomer levels increase due to phenylalanine oxidation. Several residues are oxidized in PheRS and contribute to hyperactive editing, including against mischarged Tyr-tRNA^Phe, despite these oxidized residues not …

Synthesis, Characterization And Stress-Testing Of A Robust Quillaja Saponin Stabilized Oil-In-Water Phytocannabinoid Nanoemulsion, Abhinandan Banerjee, Justin Binder, Rayan Salama, John F. Trant

Chemistry and Biochemistry Publications

Background

This study describes the design, optimization, and stress-testing of a novel phytocannabinoid nanoemulsion generated using high-pressure homogenization.QNaturale®" role="presentation">QNaturale®, a plant-derived commercial emulsifier containing quillaja saponin, was used to stabilize the lipid phase droplets in water. Stress-testing was performed on this nanoemulsion in order to evaluate its chemical and colloidal stability under the influence of different environmental factors, encompassing both physical and chemical stressors.

Methods

Extensive optimization studies were conducted to arrive at an ideal nanoemulsion formulation. A coarse emulsion containing 16.6 wt% CBD-enriched cannabis distillate and 83.4 wt% carrier (soybean) oil dispersed in 10 wt%QNaturale®" role="presentation">QNaturale®

(1.5 …

Loren Haarsma - When Did Sin Begin?, Loren Haarsma

University Faculty Publications and Creative Works

Patrick Hamilton speaks to Calvin University Professor, Loren Haarsma, about the origins of sin and various ways to make sense of the doctrine of original sin in light of evolutionary origins. Other topics of conversation include psychology, free will and the theology of Saint Augustine.

Small Studies, Big Decisions: The Role Of Pilot/Feasibility Studies In Incremental Science And Premature Scale-Up Of Behavioral Interventions, Michael William Beets, Lauren Von Klinggraeff, Robert G. Weaver, Bridget Ryan Armstrong, Sarah Burkart

Faculty Publications

Background: Careful consideration and planning are required to establish “sufficient” evidence to ensure an investment in a larger, more well-powered behavioral intervention trial is worthwhile. In the behavioral sciences, this process typically occurs where smaller-scale studies inform larger-scale trials. Believing that one can do the same things and expect the same outcomes in a larger-scale trial that were done in a smaller-scale preliminary study (i.e., pilot/feasibility) is wishful thinking, yet common practice. Starting small makes sense, but small studies come with big decisions that can influence the usefulness of the evidence designed to inform decisions about moving forward with a …

Catechin And Other Catechol-Containing Secondary Metabolites: Bacterial Biotransformation And Regulation Of Carbohydrate Metabolism, Sara Knezevic, Asma Ghafoor, Samaneh Mehri, Ali Barazi, Maksymilian Dziura, John F. Trant, Christopher A. Dieni

Chemistry and Biochemistry Publications

Background: Catechol, 1,2-dihydroxybenzene, prepared through bacterial biotransformation from higher order polyphenols, has been proposed to regulate carbohydrate metabolism, especially in the context of type 2 diabetes. This review aims to contextualize this finding. It describes the bacterial biosynthesis of catechol both from glucose, and as a degradation product of higher order natural products through bacterial transformation. The review then considers the mechanism of action of glycemic-regulating catechol-containing materials and the complications arising from balancing their inherent activity with that of catechol, their common degradation product. It then enumerates potential dietary sources of catechin from common foods. Methods: Articles were found …

Encirclement Of Moving Targets Using Noisy Range And Bearing Measurements, Cammy Peterson, Puneet Jain, Randal Beard

Faculty Publications

This paper presents theoretically justified controllers that use relative range and bearing measurements to steer a team of autonomous vehicles, operating without inertial position information, to circular trajectories around a constant-acceleration, constant-velocity, or stationary target. An extended Kalman filter is used to improve the noisy relative measurements and estimate the velocity of the moving target. These estimated values are used in the control laws to encircle constant-velocity moving targets. Lyapunov techniques are utilized to show that the vehicle will converge to the desired circular formations. Additionally, cooperating vehicles are shown to converge to a circular formation with equal temporal spacing …

Sd2 Ptov1 Interactomics, Joshua Andersen

ScholarsArchive Data

PTOV1 interactome data

Sd3 Ptov1 Ptms, Joshua Andersen

ScholarsArchive Data

MS data on PTOV1 PTMs

Sd1 14-3-3 Interactome For Ptov1 Manuscript, Joshua Andersen

ScholarsArchive Data

14-3-3 interactome

Sd1 14-3-3 Interactome For Ptov1 Manuscript, Joshua Andersen

ScholarsArchive Data

Excel data sheet of MS data from 14-3-3 interactomics

Bridging The 12-6-4 Model And The Fluctuating Charge Model, Pengfei Li

Chemistry: Faculty Publications and Other Works

Metal ions play important roles in various biological systems. Molecular dynamics (MD) using classical force field has become a popular research tool to study biological systems at the atomic level. However, meaningful MD simulations require reliable models and parameters. Previously we showed that the 12-6 Lennard-Jones nonbonded model for ions could not reproduce the experimental hydration free energy (HFE) and ion-oxygen distance (IOD) values simultaneously when ion has a charge of +2 or higher. We discussed that this deficiency arises from the overlook of the ion-induced dipole interaction in the 12-6 model, and this term is proportional to 1/r …

A Kinetic Model For Blood Biomarker Levels After Mild Traumatic Brain Injury, Sima Azizi, Daniel B. Hier, Blaine Allen, Tayo Obafemi-Ajayi, Gayla R. Olbricht, Matthew S. Thimgan, Donald C. Wunsch

Mathematics and Statistics Faculty Research & Creative Works

Traumatic brain injury (TBI) imposes a significant economic and social burden. The diagnosis and prognosis of mild TBI, also called concussion, is challenging. Concussions are common among contact sport athletes. After a blow to the head, it is often difficult to determine who has had a concussion, who should be withheld from play, if a concussed athlete is ready to return to the field, and which concussed athlete will develop a post-concussion syndrome. Biomarkers can be detected in the cerebrospinal fluid and blood after traumatic brain injury and their levels may have prognostic value. Despite significant investigation, questions remain as …