Chemistry Commons^™

Electrodeposition Of Cobalt From Eutectic-Based Ionic Liquid, Rostom Ali M., Sankar Saha S, Ziaur Rahman Md

Journal of Electrochemistry

The electrodeposition of cobalt from a solution containing cobalt chloride in either a urea-choline chloride based or an ethylene glycol (EG)-choline chloride based ionic liquid has been carried out onto copper and steel cathodes by constant current and constant potential methods at different temperatures. The influences of various experimental conditions on electrodeposition and morphology of the deposited layers have been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD)technique. It has been shown that the smooth, shiny with good adherence and bright metallic coloured cobalt coatings were obtained from both urea and EG based ionic liquids at the applied …

Electrochemical Deposition Of Cr From Cr(Iii)-Based [Bmim]Hso4 And Naoac Electrolyte, De-Ying Liu, Wei Luo, Wen-Juan Zhang, Shuo-Zhen Hu, Heng Xu, Xin-Sheng Zhang

Journal of Electrochemistry

Using trivalent chromium ions (Cr(III)) as the chromium source for chromium electrodeposition has attracted much attention since it can reduce the toxicity of the whole process. Even though the chromium deposition in Cr(III)-based ionic liquid bath can avoid the most hydrogen evolution problem, CrCl₃·6H₂O is widely used as the Cr(III) precursor, which still contains water and has the stable octahedral structure. As a result, it is difficult to deposit Cr and there is still hydrogen evolution reaction (HER). Moreover, the hydroxyl ions (OH^-) produced during HER react with Cr³⁺ to form Cr(OH)_{3 …}

About Antioxidant Activity Of Some Representatives Of Flora Of The Fergana Valley, К.А. Zahidov, S.D. Aronbaev, G.M. Abilkasimova

Scientific Journal of Samarkand University

The article presents the results of the determination of the antioxidant activity of aqueous and alcoholic extracts of 18 medicinal plants growing in the Fergana Valley using an electrochemical analyzer Σ - AOA. A solution containing 0.005 M K3 [Fe (CN) 6] and 0.001M K4 [Fe (CN) 6] in 0.05 M phosphate buffer with a pH of 6.86 was used as an electrochemically reversible mediator system. The standard of antioxidant activity was an aqueous and alcoholic solut ion of ascorbic acid with a known concentration. It was shown that all of the studied plants possess antioxidant activity to some extent. …

Molten-Salt Synthesis Of Complex Metal Oxide Nanoparticles, Jose P. Zuniga, Maya Abdou, Santosh K. Gupta, Yuanbing Mao

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we …

Primary Emissions Of Glyoxal And Methylglyoxal From Laboratory Measurements Of Open Biomass Burning, Kyle J. Zarzana, Vanessa Selimovic, Abigail R. Koss, Kanako Sekimoto, Matthew M. Coggon, Bin Yuan, William P. Dubé, Robert J. Yokelson, Carsten Warneke, Joost A. De Gouw, James M. Roberts, Steven S. Brown

Chemistry and Biochemistry Faculty Publications

We report the emissions of glyoxal and methylglyoxal from the open burning of biomass during the NOAA-led 2016 FIREX intensive at the Fire Sciences Laboratory in Missoula, MT. Both compounds were measured using cavity-enhanced spectroscopy, which is both more sensitive and more selective than methods previously used to determine emissions of these two compounds. A total of 75 burns were conducted, using 33 different fuels in 8 different categories, providing a far more comprehensive dataset for emissions than was previously available. Measurements of methylglyoxal using our instrument suffer from spectral interferences from several other species, and the values reported here …

From The River To The Gulf: An Investigation Of Biogeochemical Cycling In Wetland Soils And Coastal Shelf Sediments, Katie Bowes

LSU Master's Theses

Louisiana is home to 40% of the coastal wetlands in the lower 48 states, yet accounts for 80% of the coastal wetland loss in this region. This loss is attributed to decreased sediment supply, levee alteration, sea level rise, channelization, and subsidence. The levee system in Louisiana disconnected coastal wetlands from the main stem of the Mississippi River (MSR), reducing the amount of land-building sediment that reaches coastal wetlands. This disconnection also allows a greater percentage of river discharge, including agricultural contaminants and runoff, to flow into the northern Gulf of Mexico (NGOM).

The 2012 Coastal Master Plan proposed eight …

A Redox Conjugated Polymer-Based All-Solid-State Reference Electrode, Ke Qu, Mingxi Fang, Shuwei Zhang, Haiying Liu, Xiangqun Zeng

Department of Chemistry Publications

This work reports the design, synthesis, and characterization of a novel redox-active conjugated polyaniline containing quinone moiety as a solid state reference electrode. The union of electro-active quinone with π-conjugated polyaniline was created by the first chemical synthesis of para-dimethoxybenzene-functionalized aniline as a monomer using a palladium-mediated coupling. The successful polymerization of the as-prepared monomer was accomplished without acid additives. Its post-polymerization modification with strong Lewis acid boron tribromide furnished unique poly (aniline quinone/hydroquinone) with desired properties for all-solid-state reference electrode (RE) applications. The electrochemical responses from the conjugated polyaniline backbone in this unique polymer have been “suppressed” by the …

Starch Synthesis In Ostreococcus Tauri: The Starch-Binding Domains Of Starch Synthase Iii-B Are Essential For Catalytic Activity, Julieta Barchiesi, Maria Belen Velazquez, Nicolas Palopoli, Alberto A. Iglesias, Diego F. Gomez-Casati, Miguel A. Ballicora, Maria Victoria Busi

Chemistry: Faculty Publications and Other Works

Starch is the major energy storage carbohydrate in photosynthetic eukaryotes. Several enzymes are involved in building highly organized semi-crystalline starch granules, including starch-synthase III (SSIII), which is widely conserved in photosynthetic organisms. This enzyme catalyzes the extension of the α-1,4 glucan chain and plays a regulatory role in the synthesis of starch. Interestingly, unlike most plants, the unicellular green alga Ostreococcus tauri has three SSIII isoforms. In the present study, we describe the structure and function of OsttaSSIII-B, which has a similar modular organization to SSIII in higher plants, comprising three putative starch-binding domains (SBDs) at the N-terminal region and …

Magnetic Ordering In A Vanadium-Organic Coordination Polymer Using A Pyrrolo[2,3-D:5,4-D']Bis(Thiazole)-Based Ligand, Yulia A. Getmanenko, Christopher S. Mullins, Vladimir N. Nesterov, Stephanie Lake, Chad Risko, Ezekiel Johnston-Halperin

Chemistry Faculty Publications

Here we present the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature T_C of ∼110 K, a coercive field of ∼5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)_~2 (V·(TCNE)_~2). This material was prepared using a new tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]bis(thiazole) (C₆-PBTz). Single crystal X-ray diffraction of the 2,6-diiodo derivative of the parent C₆-PBTz, showed a disordered hexyl chain and …

Evaluating The Extent Of A Large-Scale Transformation In Gateway Science Courses, Rebecca L. Matz, Cori L. Fata-Hartley, Lynmarie A. Posey, James T. Laverty, Sonia M. Underwood, Justin H. Carmel, Deborah Herrington, Ryan L. Stowe, Marcos D. Caballero, Diane Ebert-May, Melanie M. Cooper

Peer Reviewed Articles

We evaluate the impact of an institutional effort to transform undergraduate science courses using an approach based on course assessments. The approach is guided by A Framework for K-12 Science Education and focuses on scientific and engineering practices, crosscutting concepts, and core ideas, together called three-dimensional learning. To evaluate the extent of change, we applied the Three-dimensional Learning Assessment Protocol to 4 years of chemistry, physics, and biology course exams. Changes in exams differed by discipline and even by course, apparently depending on an interplay between departmental culture, course organization, and perceived course ownership, demonstrating the complex nature of transformation …

Calculation Guided Rational Design And Synthesis Of Novel Cationic Fluorescent Meso–Pyridinium Bodipys For Bio-Imaging, Daniel J. Lamaster

LSU Doctoral Dissertations

Chapter 1 contains a brief overview of the history, synthesis, and properties of BODIPY dyes as well as that of the biomedical applications of bio-imaging and photodynamic therapy. Additionally, an overview of the theoretical framework of density functional theory and its time-dependent variant are provided. In Chapter 2, the effects of structural modification on the electronic structure and electron dynamics of cationic meso-(4-pyridyl)-BODIPYs were investigated. A library of 2,6-difunctionalized meso-(4-pyridyl)-BODIPYs bearing various electron-withdrawing substituents was designed and DFT calculations were used to model the redox properties, while TDDFT was used to determine the effects of functionalization on the excited …

Eddy Flux Measurements Of Sulfur Dioxide Deposition To The Sea Surface, Jack G. Porter, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide (SO2). The air–sea transfer of SO2 is controlled entirely on the atmospheric side of the air–sea interface due to high effective solubility and other physical– chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast-response measurements of highly soluble trace gases at very low ambient levels. In this study, we report direct eddy covariance air–sea flux measurements of SO2, sensible heat, water vapor, and momentum. The measurements were made over …

Influence Of Salinity, Sunlight, And Sediment On The Toxicity Of Pesticides In Three Non-Target Organisms, Emily Noelle Vebrosky

LSU Doctoral Dissertations

Pesticides used in the United States must undergo registration by the United States Environmental Protection Agency (USEPA), after a multitude of analyses ranging from environmental fate to aquatic toxicological impacts to human risk exposure. Testing varies for each chemical, some requiring more testing than others. In many cases, environmental factors are restricted in the analysis of chemical behavior and organismal testing is limited to larvae. Many pesticides are formulated to breakdown in the environment by means of photolysis, hydrolysis, or oxidation, either to ensure low-persistence, limited transport, or to form the active ingredient (pro-pesticides). Environmental influences on chemical behaviors include …

A Near-Infrared Fluorescent Probe Based On A Fret Rhodamine Donor Linked To A Cyanine Acceptor For Sensitive Detection Of Intracellular Ph Alternations, Yibin Zhang, Jianheng Bi, Shuai Xia, Wafa Mazi, Shulin Wan, Logan Mikesell, Rudy Luck, Haiying Liu

Department of Chemistry Publications

A fluorescence resonance energy transfer (FRET)-based near-infrared fluorescent probe (B⁺) for double-checked sensitive detection of intracellular pH changes has been synthesized by binding a near-infrared rhodamine donor to a near-infrared cyanine acceptor through robust C-N bonds via a nucleophilic substitution reaction. To demonstrate the double-checked advantages of probe B⁺, a near-infrared probe (A) was also prepared by modification of a near-infrared rhodamine dye with ethylenediamine to produce a closed spirolactam residue. Under basic conditions, probe B⁺ shows only weak fluorescence from the cyanine acceptor while probe A displays nonfluorescence due to retention of the closed …

Metallo-Polyelectrolytes As A Class Of Ionic Macromolecules For Functional Materials, Tianyu Zhu, Ye Sha, Jing Yan, Parasmani Pageni, Md Anisur Rahman, Yi Yan, Chuanbing Tang

Faculty Publications

The fields of soft polymers and macromolecular sciences have enjoyed a unique combination of metals and organic frameworks in the name of metallopolymers or organometallic polymers. When metallopolymers carry charged groups, they form a class of metal-containing polyelectrolytes or metallo-polyelectrolytes. This review identifies the unique properties and functions of metallo-polyelectrolytes compared with conventional organo-polyelectrolytes, in the hope of shedding light on the formation of functional materials with intriguing applications and potential benefits. It concludes with a critical perspective on the challenges and hurdles for metallo-polyelectrolytes, especially experimental quantitative analysis and theoretical modeling of ionic binding.

Liquid Phenothiazine Catholytes For Non-Aqueous Redox Flow Batteries, Susan A. Odom, Matthew D. Casselman, Aman Preet Kaur

Chemistry Faculty Patents

Highly soluble, liquid phenothiazines containing methoxy-terminated ether and oligoether substituents are disclosed with high diffusion coefficients and robust performance in electrochemical measurements, which can be synthesized in one step from commercially-available starting materials, thereby circumventing previous synthetic limitations.

On The Roles Of Wheat Endosperm Adp-Glucose Pyrophosphorylase Subunits, Danisa M. L. Ferrero, Matias D. Asencion Diez, Misty L. Kuhn, Christine A. Falaschetti, Claudia V. Piattoni, Alberto A. Iglesias, Miguel A. Ballicora

Chemistry: Faculty Publications and Other Works

The ADP-glucose pyrophosphorylase from wheat endosperm controls starch synthesis in seeds and has unique regulatory properties compared to others from this family. It comprises two types of subunits, but despite its importance little is known about their roles. Here, we synthesized de novo the wheat endosperm ADP-glucose pyrophosphorylase small (S) and large (L) subunit genes, heterologously expressed them in Escherichia coli, and kinetically characterized the recombinant proteins. To understand their distinct roles, we co-expressed them with well characterized subunits from the potato tuber enzyme to obtain hybrids with one S subunit from one source and an L subunit from …

Resveratrol Sustains Insulin-Degrading Enzyme Activity Toward Aβ42, Claire A. Krasinski, Valerie A. Ivancic, Qiuchen Zheng, Donald E. Spratt, Noel D. Lazo

Chemistry

Alzheimer's disease (AD), the most common cause of dementia in the elderly, is the sixth leading cause of death in the United States. We hypothesize that the impaired clearance of Aβ42 from the brain is partly responsible for the onset of sporadic AD. In this work, we evaluated the activity of insulin-degrading enzyme (IDE) toward Aβ42 in the presence of resveratrol, a polyphenol found in red wine and grape juice. By liquid chromatography/mass spectrometry, we identified initial cleavage sites in the absence and presence of resveratrol that carry biological relevance connected to the amyloidogenic properties of Aβ42. Incubation with resveratrol …

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic …

Speciated Online Pm1 From South Asian Combustion Sources-Part 1: Fuel-Based Emission Factors And Size Distributions, J. Douglas Goetz, Michael R. Giordano, Chelsea E. Stockwell, Ted J. Christian, Rashmi Maharjan, Sagar Adhikari, Prakash V. Bhave, Puppala S. Praveen, Arnico K. Panday, Thilina Jayarathne, Elizabeth A. Stone, Robert J. Yokelson, Peter F. Decarlo

Chemistry and Biochemistry Faculty Publications

Combustion of biomass, garbage, and fossil fuels in South Asia has led to poor air quality in the region and has uncertain climate forcing impacts. Online measurements of submicron aerosol (PM1) emissions were conducted as part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) to investigate and report emission factors (EFs) and vacuum aerodynamic diameter (dva) size distributions from prevalent but poorly characterized combustion sources. The online aerosol instrumentation included a qmini aerosol mass spectrometer (mAMS) and a dual-spot eight-channel aethalometer (AE33). The mAMS measured non-refractory PM1 mass, composition, and size. The AE33-measured black carbon (BC) mass and …

Novel Antibacterial Compounds And Methods Of Making And Using Same, Amit Basu, Christopher W. Reid, Mary Margaret O'Connor, Ethan Lindsay Magno, Mitchell Evan Jamieson, Ryan Daniel Miller

Science and Technology Department Faculty Journal Articles

No abstract provided.

Unexpected Effects Of Inorganic Phosphate Glass On Crystallization And Thermo-Rheological Behavior Of Polyethylene Terephthalate, Kyoungtae Kim, Shahab Kashani Rahimi, Todd M. Alam, Eric G. Sorte, Joshua U. Otaigbe

Faculty Publications

The effects of ultra-low glass transition temperature (T_g) phosphate glass (Pglass) on the thermal, morphological, rheological, mechanical, and crystallization properties of hybrid Pglass/poly(eththylene terephthalate)(PET) were investigated. Nano- and micro-scale distribution of the Pglass in the PET polymer matrix was observed. The polydispersed Pglass in the PET matrix functioned as a nucleation agent, resulting in increasing crystallization temperature. The Pglass in the PET matrix decreased the T_g, indicating a plasticizing effect of the Pglass in the hybrids that was confirmed by the significantly decreased complex viscosity of the PET matrix. In addition, with increasing temperature, a non-terminal …

Reactive Iron Mineral Coatings In Redox Transition Zones And Their Impact On Natural Attenuation, Lisa Axe

Sustainability Seminar Series

Reactive Fe mineral coatings play an important role in contaminant attenuation in redox transition zones at sites with subsurface contamination. An anaerobic 60 foot core was collected from the Chambers Works Site in Deepwater, NJ. Working in a glovebox, two-inch subsamples were used to evaluate redox transition zones using bulk composition, redox potential, pH, VOCs in the headspace, as well as abundant bacteria. A number of redox transition zones were identified and further studied with a suite of complementary analyses to characterize the surface chemistry. Analyses have included sequential extraction (phases and speciation), x-ray diffraction (mineralogy), x-ray fluorescence (composition), fieldemission …

Reaction Optimization Of Pyrazinoquinoxaline Based Organic Semiconductor With Cruciform Shape, Marco Valverde Paredes, Dong-Chan Lee

LSAMP Poster Presentations

In this work, an optimum reaction condition was established to synthesize a pyrazinoquinoxaline based organic semiconductor with cruciform shape.

Multielectron Redox Chemistry Of Transition Metal Complexes Supported By A Non‐Innocent N3p2 Ligand: Synthesis, Characterization, And Catalytic Properties, Denan Wang, Danushka M. Ekanayake, Sergey V. Lindeman, Cláudio N. Verani, Adam T. Fiedler

Chemistry Faculty Research and Publications

A new redox‐active, diarylamido‐based ligand (L^N3P2) capable of κ⁵‐N,N,N,P,P chelation has been used to prepare a series of complexes with the general formula [M^II(L^N3P2)]X, where M = Fe (1; X = OTf), Co (2; X = ClO₄), or Ni (3; X = ClO₄). The diarylamido core of monoanionic L^N3P2 is derived from bis(2‐amino‐4‐methylphenyl)amine, which undergoes condensation with two equivalents of 2‐(diphenylphosphanyl)benzaldehyde to provide chelating arms with both arylphosphine and imine donors. X‐ray structural, magnetic, …

Synthesis And Characterization Of Transition Metal Based Nanocomposites For Orr In Fuel Cell Applications, Hunter Austin Wayland

Theses and Dissertations

Development of economically viable platinum alternatives for polymer electrolyte membrane fuel cells is a fundamental step towards large-scale commercialization efforts, which aim to reduce reliance on non-renewable energy resources. This work explores the synthesis, characterization, and application of graphene supported cobalt(III) and iron(III) based MN4 complexes for oxygen reduction, and farther investigates the potential for gains in performance and enhanced stability following coating with a bioinspired self- assembling polymer, polydopamine. The nanocomposites were characterized using a variety of electron microscopy and spectroscopy techniques, and their electrochemical performance was assessed using a potentiostat/galvanostat. The polymer-uncoated nanocomposites were found to reduce oxygen …

Au@H-Al2o3 Analogic Yolk–Shell Nanocatalyst For Highly Selective Synthesis Of Biomass-Derived D-Xylonic Acid Via Regulation Of Structure Effects, Jiliang Ma, Zewei Liu, Junlong Song, Linxin Zhong, Dequan Xiao, Hongxia Xi, Xuehui Li, Runcang Sun, Xinwen Peng

Chemistry and Chemical Engineering Faculty Publications

Selective oxidation of biomass-based monosaccharides into value-added sugar acids is highly desired, but limited success of producing D-xylonic acid has been achieved. Herein, we report an efficient catalyst system, viz., Au nanoparticles anchored on the inner walls of hollow Al₂O₃ nanospheres (Au@h- Al₂O₃), which could catalyze the selective oxidation of D-xylose into D-xylonic acid under base-free conditions. The mesoporous Al₂O₃ shell as the adsorbent first adsorbed D-xylose. Then, the interface of Au nanoparticles and Al₂O₃ as active sites spontaneously dissociated O₂, and …

Influence Of Phosphate On Tungstate Sorption On Hematite: A Macroscopic And Spectroscopic Evaluation Of The Mechanism, Bryan Sallman, Sudipta Rakshit, Grégory Lefèvre

Agricultural and Environmental Sciences Faculty Research

The environmental fate of the tungstate (VI) oxyanion [ e.g. mono tungstate and several polytungstate, generally expressed by W (VI)] is largely controlled by sorption on soil minerals, especially on iron oxide minerals. Molecular scale evaluation of W (VI) retention on iron oxides in the presence of competing oxyanions is scarce in literature. Here we report surface interaction mechanisms of W (VI) on hematite in the presence of phosphate (P) using macroscopic and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic experiments. Batch sorption experiments were conducted using 2 g L−1 hematite and 100 μM W (VI) and …

Molecular And Physical Characteristics Of Aerosol At A Remote Free Troposphere Site: Implications For Atmospheric Aging, Simeon Schum, Bo Zhang, Katja Džepina, Paolo Fialho, Claudio Mazzoleni, Lynn Mazzoleni

Department of Chemistry Publications

Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of …

Phosphonium Hydrogels For Controlled Release Of Ionic Cargo., Tristan D Harrison, Paul J Ragogna, Elizabeth R Gillies

Chemistry Publications

We describe the synthesis of three different phosphonium salts and their reaction with poly(ethylene glycol) dimethacrylate to create cationic hydrogels. The hydrogels were loaded with an anionic dye and an anionic anti-inflammatory drug through ionic interactions and compared with an analogous ammonium gel. The release rates of these anions depended on their structure and pKa values, as well as the pH and ionic strength of the release medium.