Physical Sciences and Mathematics Commons^™

Photoluminescence Switching In Quantum Dots Connected With Fluorinated And Hydrogenated Photochromic Molecules, Ephraiem S. Sarabamoun, Jonathan M. Bietsch, Pramod Aryal, Amelia G. Reid, Maurice Curran, Grayson Johnson, Esther H. R. Tsai, Charles W. Machan, Guijun Wang, Joshua J. Choi

Chemistry & Biochemistry Faculty Publications

We investigate switching of photoluminescence (PL) from PbS quantum dots (QDs) crosslinked with two different types of photochromic diarylethene molecules, 4,4'-(1-cyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (1H) and 4,4'-(1-perfluorocyclopentene-1,2-diyl)bis[5-methyl-2-thiophenecarboxylic acid] (2F). Our results show that the QDs crosslinked with the hydrogenated molecule (1H) exhibit a greater amount of switching in photoluminescence intensity compared to QDs crosslinked with the fluorinated molecule (2F). With a combination of differential pulse voltammetry and density functional theory, we attribute the different amount of PL switching to the different energy levels between 1H and 2F molecules which result in different potential barrier …

Reduced Metal Nanocatalysts For Selective Electrochemical Hydrogenation Of Biomass-Derived 5-(Hydroxymethyl)Furfural To 2, 5-Bis(Hydroxymethyl)Furan In Ambient Conditions, Baleeswaraiah Muchharla, Moumita Dikshit, Ujjwal Pokharel, Ravindranath Garimella, Adetayo Adedeji, Kapil Kumar, Wei Cao, Hani Elsayed-Ali, Kishor Kumar Sadasivuni, Naif Abdullah Al-Dhabi, Sandeep Kumar, Bijandra Kumar

Chemistry & Biochemistry Faculty Publications

Selective electrochemical hydrogenation (ECH) of biomass-derived unsaturated organic molecules has enormous potential for sustainable chemical production. However, an efficient catalyst is essential to perform an ECH reaction consisting of superior product selectivity and a higher conversion rate. Here, we examined the ECH performance of reduced metal nanostructures i.e., reduced Ag (rAg) and reduced copper (rCu) prepared via electrochemical or thermal oxidation and electrochemical reduction process, respectively. Surface morphological analysis suggests formation of nanocoral and entangled nanowire structure formation for rAg and rCu catalysts. rCu exhibits slight enhancement in ECH reaction performance in comparison to the pristine Cu. However, the rAg …

Insights Into The Deglacial Variability Of Phytoplankton Community Structure In The Eastern Equatorial Pacific Ocean Using [231Pa/230Th]Xs And Opal-Carbonate Fluxes, Danielle Schimmenti, Franco Marcantonio, Christopher T. Hayes, Jennifer Hertzberg, Matthew Schmidt, John Sarao

OES Faculty Publications

Fully and accurately reconstructing changes in oceanic productivity and carbon export and their controls is critical to determining the efficiency of the biological pump and its role in the global carbon cycle through time, particularly in modern CO₂ source regions like the eastern equatorial Pacific (EEP). Here we present new high-resolution records of sedimentary ²³⁰Th-normalized opal and nannofossil carbonate fluxes and [²³¹Pa/²³⁰Th]xs ratios from site MV1014-02-17JC in the Panama Basin. We find that, across the last deglaciation, phytoplankton community structure is driven by changing patterns of nutrient (nitrate, iron, and silica) availability which, in …

Stimuli-Responsive Gelators From Carbamoyl Sugar Derivatives And Their Responses To Metal Ions And Tetrabutylammonium Salts, Dan Wang, Anji Chen, Joedian Morris, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Carbohydrate-based low molecular weight gelators (LMWGs) are interesting compounds with a variety of applications. In this research, a library of nineteen carbamate derivatives of N-acetyl-D-glucosamine were synthesized and characterized, and several derivatives were found to be effective LMWGs. They formed gels in pump oils as well as mixtures of water with ethanol or water with DMSO. The structures of the carbamoyl chains played an important role in the gelation properties, short chain aliphatic derivatives and phenyl carbamates formed gels in more solvents than certain aromatic and dimeric carbamates. The phenyl carbamate gelator was also selected for the encapsulation of …

Surface Oxygenation Of Biochar Through Ozonization For Dramatically Enhancing Cation Exchange Capacity, Matthew D. Huff, Sarah Marshall, Haitham A. Saeed, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Background

Biochar cation exchange capacity (CEC) is a key property that is central to biochar environmental applications including the retention of soil nutrients in soil amendment and removal of certain pollutants in water-filtration applications.

Results

This study reports an innovative biochar-ozonization process that dramatically increases the CEC value of biochars by a factor of 2. The ozonized biochars also show great improvement on adsorption of methylene blue by as much as a factor of about 5. In this study, biochar samples treated with and without ozone were analyzed by means of pH and CEC assays, water field capacity measurement, elemental …

Perspectives On Chemical Oceanography In The 21st Century: Participants Of The Come Aboard Meeting Examine Aspects Of The Field In The Context Of 40 Years Of Disco, Andrea J. Fassbender, Hilary I. Palevsky, Todd R. Martz, Anitra E. Ingalls, Martha Gledhill, Sarah E. Fawcett, Jay A. Brandes, Lihini I. Aluwihare, The Participants Of Come Aboard, Disco Xxv

OES Faculty Publications

The questions that chemical oceanographers prioritize over the coming decades, and the methods we use to address these questions, will define our field's contribution to 21st century science. In recognition of this, the U.S. National Science Foundation and National Oceanic and Atmospheric Administration galvanized a community effort (the Chemical Oceanography MEeting: A BOttom-up Approach to Research Directions, or COME ABOARD) to synthesize bottom-up perspectives on selected areas of research in Chemical Oceanography. Representing only a small subset of the community, COME ABOARD participants did not attempt to identify targeted research directions for the field. Instead, we focused on how best …

Phytoplankton Plastid Proteomics: Cracking Open Diatoms To Understand Plastid Biochemistry Under Iron Limitation, Skyler J. Nunn, Phoebe Dreux Chappell, Kristofer Gomes, Anasthasia Bonderenko, Bethany D. Jenkins, Brook L. Nunn

OES Faculty Publications

Diatoms, such as Thalassiosira pseudonana, are important oceanic primary producers, as they sequester carbon dioxide (CO₂) out of the atmosphere, die, and precipitate to the ocean floor. In many areas of the world’s oceans, phytoplankton, such as diatoms, are limited in growth by the availability of iron (Fe). Fe is an essential nutrient for phytoplankton, as it is central in the electron transport chain component of photosynthesis. Through this study, we examined if Fe-limitation makes a significant difference in the proteins expressed within the chloroplast, the power source for diatoms. Here, we utilized a new plastid isolation technique specific …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

Characterization Of Biochars Produced From Peanut Hulls And Pine Wood With Different Pyrolysis Conditions, James W. Lee, Bob Hawkins, Michelle K. Kidder, Barbara R. Evans, A. C. Buchanan, Danny Day

Chemistry & Biochemistry Faculty Publications

Background

Application of modern biomass pyrolysis methods for production of biofuels and biochar is potentially a significant approach to enable global carbon capture and sequestration. To realize this potential, it is essential to develop methods that produce biochar with the characteristics needed for effective soil amendment.

Methods

Biochar materials were produced from peanut hulls and pine wood with different pyrolysis conditions, then characterized by cation exchange (CEC) capacity assays, nitrogen adsorption–desorption isotherm measurements, micro/nanostructural imaging, infrared spectra and elemental analyses.

Results

Under a standard assay condition of pH 8.5, the CEC values of the peanut hull-derived biochar materials, ranging from …

Satellite Observations Of Stratospheric Hydrogen Flouride And Comparisons With Slimcat Calculations, Jeremy J. Harrison, Martyn P. Chipperfield, Christopher D. Boone, Sandip S. Dhomse, Peter F. Bernath, Lucien Froidevaux

Chemistry & Biochemistry Faculty Publications

The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of hydrogen fluoride (HF), the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing …

Plant Species Rather Than Climate Greatly Alters The Temporal Pattern Of Litter Chemical Composition During Long-Term Decomposition, Yongfu Li, Na Chen, Mark E. Harmon, Yuan Li, Xiaoyan Cao, Mark A. Chappell, Jingdong Mao

Chemistry & Biochemistry Faculty Publications

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, …

Technical Note: Swift - A Fast Semi-Empirical Model For Polar Stratospheric Ozone Loss, M. Rex, S. Kremser, P. Huck, G. Bodeker, I. Wohltmann, M. L. Santee, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

An extremely fast model to estimate the degree of stratospheric ozone depletion during polar winters is described. It is based on a set of coupled differential equations that simulate the seasonal evolution of vortex-averaged hydrogen chloride (HCl), nitric acid (HNO3), chlorine nitrate (ClONO₂), active forms of chlorine (ClO_x = Cl+ClO+2ClOOCl) and ozone (O₃) on isentropic levels within the polar vortices. Terms in these equations account for the chemical and physical processes driving the time rate of change of these species. Eight empirical fit coefficients associated with these terms are derived by iteratively fitting the equations …

Middle Atmospheric Changes Caused By The January And March 2012 Solar Proton Events, C. H. Jackman, C. E. Randall, V. L. Harvey, S. Wang, E. L. Fleming, M. López-Puertas, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

The recent 23-30 January and 7-11 March 2012 solar proton event (SPE) periods were substantial and caused significant impacts on the middle atmosphere. These were the two largest SPE periods of solar cycle 24 so far. The highly energetic solar protons produced considerable ionization of the neutral atmosphere as well as HOx (H, OH, HO2) and NOx (N, NO, NO2). We compute a NOx production of 1.9 and 2.1 Gigamoles due to these SPE periods in January and March 2012, respectively, which places these SPE periods among the 12 largest in the past 50 yr. Aura Microwave Limb Sounder (MLS) …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

The goal of this study is to determine how H₂O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H₂O characteristics that are robust across data sets and that can be used to evaluate …

Simulations Of Nanopore Formation And Phosphatidylserine Externalization In Lipid Membranes Subjected To A High-Intensity, Ultrashort Electric Pulse, Q. Hu, R. P. Joshi, K. H. Schoenbach

Bioelectrics Publications

A combined MD simulator and time dependent Laplace solver are used to analyze the electrically driven phosphatidylserine externalization process in cells. Time dependent details of nanopore formation at cell membranes in response to a high-intensity (100kV∕cm), ultrashort (10ns) electric pulse are also probed. Our results show that nanosized pores could typically be formed within about 5ns. These predictions are in very good agreement with recent experimental data. It is also demonstrated that defect formation and PS externalization in membranes should begin on the anode side. Finally, the simulations confirm that PS externalization is a nanopore facilitated event, rather than the …