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At least 307 records · Page 17

Dye Aggregation and Complex Formation Effects in 7-(Diethylamino)-coumarin-3-carboxylic Acid

7-(Diethylamino)-coumarin-3-carboxylic acid (1) has been used as a laser dye, fluorescent label, and biomedical inhibitor in many different applications. Although this dye is typically used in the solution phase, it is prone to molecular aggregation, resulting in many inconsistent optoelectronic properties being reported in the literature. In this paper, the UV—vis absorption and fluorescence spectra of 1 are investigated in three representative solvents: cyclohexane [nonpolar and non-hydrogen bonding (NHB)], ethanol (moderately polar and hydrogen-bond accepting/donating), and DMSO (strongly polar and hydrogen-bond accepting). These experimental results, in conjunction with (time-dependent) density functional theory (DFT/TDDFT) based quantum calculations, have led to the identification of the J-aggregates of 1, and rationalized its different aggregation characteristic in cyclohexane in contrast to that of another similar compound, coumarin 343. We show here that these aggregates are largely responsible for the anomalous optoelectronic properties of this compound. In addition, DFT calculations and 1H NMR spectroscopy measurements suggest that the intramolecular hydrogen bond in 1 could be "opened up" in hydrogen-bond accepting solvents, affording significant molecular conformational changes and complex formation effects. The comprehensive understanding of the molecular aggregation and complex formation mechanisms of 1 acquired through this work forms a foundation for the knowledge-based molecular design of organic dyes with tailored aggregation tendencies or anti-aggregation characteristics to cater for different opapplications.

Liu, Xiaogang↗

Data Fusion via Neural Network Entropy Minimization for Target Detection and Multi-Sensor Event Classification

Broadly applicable solutions to multimodal and multisensory fusion problems across domains remain a challenge because effective solutions often require substantive domain knowledge and engineering. The chief questions that arise for data fusion are in when to share information from different data sources, and how to accomplish the integration of information. The solutions explored in this work remain agnostic to input representation and terminal decision fusion approaches by sharing information through the learning objective as a compound objective function. The objective function this work uses assumes a one-to-one learning paradigm within a one-to-many domain which allows the assumption that consistency can be enforced across the one-to-many dimension. The domains and tasks we explore in this work include multi-sensor fusion for seismic event location and multimodal hyperspectral target discrimination. We find that our domain- informed consistency objectives are challenging to implement in stable and successful learning because of intersections between inherent data complexity and practical parameter optimization. While multimodal hyperspectral target discrimination was not enhanced across a range of different experiments by the fusion strategies put forward in this work, seismic event location benefited substantially, but only for label-limited scenarios.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Formation of ultracold X {sup 1}{Sigma}{sup +}(v{sup ''}=0) NaCs molecules via coupled photoassociation channels

We report production of ultracold X {sup 1}{Sigma}{sup +}(v{sup ''}=0) NaCs molecules via photoassociation. We utilize a combination of spectroscopic techniques to determine formation pathways and label ground-state samples. Efficient free-bound excitation occurs due to coupling between B {sup 1}{Pi} and neighboring electronic states in the Na 3S+Cs 6P complex. An f-wave shape resonance contributes to formation of a rotationally pure sample of X {sup 1}{Sigma}{sup +}(v{sup ''}=0,J{sup ''}=1) molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗

Peroxidase versus Peroxygenase Activity: Substrate Substituent Effects as Modulators of Enzyme Function in the Multifunctional Catalytic Globin Dehaloperoxidase

The dehaloperoxidase-hemoglobin (DHP) from the terebellid polychaete Amphitrite ornata is a multifunctional hemoprotein that catalyzes the oxidation of a wide variety of substrates, including halo/nitrophenols, haloindoles, and pyrroles, via peroxidase and/or peroxygenase mechanisms. To probe whether substrate substituent effects can modulate enzyme activity in DHP, we investigated its reactiviy against a panel of o-guaiacol substrates given their presence (from native/halogenated and non-native/anthropogenic sources) in the benthic environment that A. ornata inhabits. Using biochemical assays supported by spectroscopic, spectrometric, and structural studies, DHP was found to catalyze the H 2 O 2 -dependent oxidative dehalogenation of 4-haloguaiacols (F, Cl, and Br) to 2-methoxybenzoquinone (2-MeOBQ). 18 O labeling studies confirmed that O atom incorporation was derived exclusively from water, consistent with substrate oxidation via a peroxidase-based mechanism. Here, the 2-MeOBQ product further reduced DHP to its oxyferrous state, providing a link between the substrate oxidation and O 2 carrier functions of DHP. Nonnative substrates resulted in polymerization of the initial substrate with varying degrees of oxidation, with 2-MeOBQ identified as a minor product. When viewed alongside the reactivity of previously studied phenolic substrates, the results presented here show that simple substituent effects can serve as functional switches between peroxidase and peroxygenase activities in this multifunctional catalytic globin. More broadly, when recent findings on DHP activity with nitrophenols and azoles are included, the results presented here further demonstrate the breadth of heterocyclic compounds of anthropogenic origin that can potentially disrupt marine hemoglobins or function as environmental stressors, findings that may be important when assessing the environmental impact of these pollutants (and their metabolites) on aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simple but tricky: Investigations of terephthalic acid purity obtained from mixed PET waste

In this study, we report for the first time, the basic depolymerization of mixed waste-polyethylene terephthalate (PET) by hydrolysis and subsequent terephthalic acid monomer recovery at high purity using benign reaction conditions. Several conditions were tested for depolymerization such as PET chips size, concentration of aqueous sodium hydroxide (20 or 30%), organic co-solvent (ethylene glycol or ethanol), temperature at which the reaction was run and duration of the heating. More importantly, several batches of PET were utilized as starting materials including a commercial PET, chopped PET obtained from clean bottles whose caps and labels were removed and the purity of the product from each condition was evaluated via nuclear magnetic resonance (1HNMR and 13CNMR), differential scanning calorimetry (DSC) and powder Xray diffraction (XRD). Unsurprisingly, the conversion of PET is dependent on the particle size varying from 100% conversion for fine powder to 73% conversion for (300 µm, mesh 6 – 20 or mesh 14-20). Ethanol appears to be more efficient as a co-solvent than ethylene glycol, with higher PET depolymerization conversions (94% versus 75-80%), shorter reaction times (2h versus 6h) and lower temperatures (80 °C versus 110 °C). The terephthalic acid (TPA) recovered appeared to have only subtle differences among the batches, most notably a pink color when the reaction was run in ethanol/base. The DSC of the compounds produced in ethylene glycol water appear to display a melting point (280-288 °C) while the samples prepared in ethanol as well as a commercial sample did not. Overall, the purity of the various TPA batches is comparable, and similar to commercial TPA, demonstrating the utility of the method to depolymerize realistic waste streams. The method is simple, demonstrated on multigram scale (15-30g) and allows for the complete removal of waste other than PET unaffected by alkaline conditions.

Cosimbescu, Lelia↗

General Considerations of the Electrostatic Boundary Conditions in Oxide Heterostructures

When the size of materials is comparable to the characteristic length scale of their physical properties, novel functionalities can emerge. For semiconductors, this is exemplified by the 'superlattice' concept of Esaki and Tsu, where the width of the repeated stacking of different semiconductors is comparable to the 'size' of the electrons, resulting in novel confined states now routinely used in opto-electronics. For metals, a good example is magnetic/non-magnetic multilayer films that are thinner than the spin-scattering length, from which giant magnetoresistance (GMR) emerged, used in the read heads of hard disk drives. For transition metal oxides, a similar research program is currently underway, broadly motivated by the vast array of physical properties that they host. This long-standing notion has been recently invigorated by the development of atomic-scale growth and probe techniques, which enables the study of complex oxide heterostructures approaching the precision idealized in Fig. 1(a). Taking the subset of oxides derived from the perovskite crystal structure, the close lattice match across many transition metal oxides presents the opportunity, in principle, to develop a 'universal' heteroepitaxial materials system. Hand-in-hand with the continual improvements in materials control, an increasingly relevant challenge is to understand the consequences of the electrostatic boundary conditions which arise in these structures. The essence of this issue can be seen in Fig. 1(b), where the charge sequence of the sublayer 'stacks' for various representative perovskites is shown in the ionic limit, in the (001) direction. To truly 'universally' incorporate different properties using different materials components, be it magnetism, ferroelectricity, superconductivity, etc., it is necessary to access and join different charge sequences, labelled here in analogy to the designations 'group IV, III-V, II-VI' for semiconductors. As we will review, interfaces between different families creates a host of electrostatic issues. They can be somewhat avoided if, as in many semiconductor heterostructures, only one family is used, with small perturbations (such as n-type or p-type doping) around them. However, for most transition metal oxides, this is greatly restrictive. For example, LaMnO{sub 3} and SrMnO{sub 3} are both insulators in part due to strong electron correlations, and only in their solid solution does 'colossal magnetoresistance' emerge in bulk. Similarly, the metallic superlattice shown in Fig. 1(c) can be considered a nanoscale deconstruction of (La,Sr)TiO{sub 3} to the insulating parent compounds. Therefore the aspiration to arbitrarily mix and match perovskite components requires a basic understanding of, and ultimately control over, these issues. In this context, here we present basic electrostatic features that arise in oxide heterostructures which vary the ionic charge stacking sequence. In close relation to the analysis of the stability of polar surfaces and semiconductor heterointerfaces, the variation of the dipole moment across a heterointerface plays a key role in determining its stability. Different self-consistent assignments of the unit cell are presented, allowing the polar discontinuity picture to be recast in terms of an equivalent local charge neutrality picture. The latter is helpful in providing a common framework with which to discuss electronic reconstructions, local-bonding considerations, crystalline defects, and lattice polarization on an equal footing, all of which are the subject of extensive current investigation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The distribution of complexes {sup 69m}ZnL{sup 1}Cl{sub 2}, [{sup 69m}Zn(L{sup 2}){sub 2}]Cl{sub 2}, and [{sup 69m}Zn(L{sup 2}){sub 2}]Sal{sub 2} (L{sup 1} is N-(5,6-dihydro-4H-1,3-thiazin-2-yl)benzamide, L{sup 2} is 2-aminopyrimidine, Sal is a salicylate ion) in vivo in mice

The distribution of complexes of thiazine and pyrimidine derivatives possessing antileukemic activity and labeled with radionuclide {sup 69m}Zn in the organs of mice and its rate of excretion were studied. A solution of ZnCl{sub 2} was used for comparison. An increase in the time of excretion of the drug from the body and a decrease of its penetration into the brain in the presence of a salicylate ion were observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Airborne measurements of tropospheric ozone destruction and particulate bromide formation in the Arctic

Aircraft profiles of O3 concentrations over the Arctic ice pack in spring exhibit a depletion of O3 beneath the surface temperature inversion. One such profile from the NOAA WP-3D Arctic Gas and Aerosol Sampling Program (AGASP) flights in April, 1986 north of Alert, NWT (YLT, 82.5 N) is shown. The gradient of O3 across the temperature inversion, which is essentially a step function from tropospheric values (35 to 40 ppbv) to 0, is somewhat masked by a 1-min running mean applied to the data. Evidence is presented that O3 destruction beneath the Arctic temperature inversion is the result of a photochemical reaction between gaseous Br compounds and O3 to produce particulate Br aerosol. It is noted that in springtime, O3 at the Alert Baseline Station regularly decreases from 30 to 40 ppbv to near 0 over the period of a few hours to a day. At the same time, there is a production of particulate Br with a near 1.0 anti-correlation to O3 concentration. Surface concentrations of bromoform in the Arctic exhibit a rapid decrease following polar sunrise. AGASP aircraft measurements of filterable bromine particulates in the Arctic (March-April, 1983 and 1986) are shown. The greatest concentrations of Br aerosol (shown as enrichment factors relative to to Na in seawater, EFBR (Na)) were observed in samples collected beneath the surface temperature inversion over ice. Samples collected at the same altitude over open ocean (off Spitzbergen) labeled Marine did not exhibit similar Br enrichments. A second region of particulate Br enrichment was observed in the lower stratosphere, which regularly descends to below 500 mb (5.5 km) in the high Arctic. The NOAA WP-3D flew in the stratosphere on all AGASP flights and occasionally measured O3 concentrations in excess of 300 ppbv.

Schnell, Russell C.↗

Enhancing Docking Accuracy with PECAN2, a 3D Atomic Neural Network Trained without Co-Complex Crystal Structures

Decades of drug development research have explored a vast chemical space for highly active compounds. The exponential growth of virtual libraries enables easy access to billions of synthesizable molecules. Computational modeling, particularly molecular docking, utilizes physics-based calculations to prioritize molecules for synthesis and testing. Nevertheless, the molecular docking process often yields docking poses with favorable scores that prove to be inaccurate with experimental testing. To address these issues, several approaches using machine learning (ML) have been proposed to filter incorrect poses based on the crystal structures. However, most of the methods are limited by the availability of structure data. Here, we propose a new pose classification approach, PECAN2 (Pose Classification with 3D Atomic Network 2), without the need for crystal structures, based on a 3D atomic neural network with Point Cloud Network (PCN). The new approach uses the correlation between docking scores and experimental data to assign labels, instead of relying on the crystal structures. We validate the proposed classifier on multiple datasets including human mu, delta, and kappa opioid receptors and SARS-CoV-2 Mpro. Our results demonstrate that leveraging the correlation between docking scores and experimental data alone enhances molecular docking performance by filtering out false positives and false negatives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Smartphone-based Dual-channel Immunochromatographic Test Strip with Polymer Quantum Dot Labels for Simultaneous Detection of Cypermethrin and 3-phenoxybenzoic acid

Currently, gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) are the primary methods used to detect pesticides and their metabolites for biomonitoring of exposure. Although GC-MS and LC-MS can provide accurate and sensitive measurements, these techniques are not suitable for point-of-care or in-field biomonitoring applications. The objective of this work is to develop a smartphone-based dual-channel immunochromatographic test strip (ICTS) for on-site biomonitoring of exposure to cypermethrin by simultaneous detection of cypermethrin and its metabolite, 3-phenoxybenzoic acid (3-PBA). Polymer carbon dots (PCDs) with ultra-high fluorescent brightness were synthesized and used as signal amplifier in ICTS assay. Cypermethrin (a representative pyrethroid pesticide) and its major metabolite 3-PBA were simultaneously detected to provide more comprehensive analysis of cypermethrin exposure. After competitive immunoreactions between the target sample and the coating antigens preloaded on the test line, the tracer antibody (PCDs conjugated antibody) was quantitatively captured on the test lines. The captured PCDs were inversely proportional to the amount of the target compound in sample. The red fluorescence on the test line then was recorded by a smartphone-based device capable of conducting image analysis and recording. Under optimal conditions, the sensor showed excellent linear responses for detecting cypermethrin and 3-PBA ranging from 1 ng/mL to 100 ng/mL and from 0.1 ng/mL to 100 ng/mL, the limits of detection were calculated to be ~0.35 ng/mL for cypermethrin and ~0.04 ng/mL for 3-PBA, respectively. The results demonstrate that the ICTS device is promising for accurate point-of-care biomonitoring of pesticide exposure.

Zhao, Yuting↗

Effect of sintering time on structural, microstructural and chemical composition of Ni-doped lanthanum gallate perovskites

This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La{sub 0.90}Sr{sub 0.10}GaO{sub 3.00−δ}. Independently of the sintering time, La{sub 0.90}Sr{sub 0.10}Ga{sub 1−x}Ni{sub x}O{sub 3.00−δ} (where x=0.10, and 0.20 (mol)) presents a rhombohedral symmetry with a lattice volume that decreases when NiO dopant increases. Besides the perovskite, LaSrGa{sub 3.00}O{sub 7.00} (nominal composition) is present as second phase in all cases. When the samples are doped with NiO, the peaks of this second phase are shifted with respect to the peaks of the pure phase. These shifts suggest that this second phase could admit some Ni ions in its structure. According to the XRD patterns, the amount of the latter phase is larger when sintering time is increased. Electron probe microanalysis (EPMA) indicated that the matrix of the samples sintered for 6 h is constituted by a perovskite with an experimental composition very close to the nominal one. However, when the samples are sintered for 48 h the matrix of each sample is constituted by two perovskites; both with compositional deviations with respect to their nominal one. In particular, a significant Sr depletion compensated by a La increment in the A site is observed. Those compositional deviations could be mainly due to the diffusion of the cations in the bulk and/or from the bulk to the surface of the samples. That diffusion can favour the formation, not only, of a second perovskite with a different composition in relation with the first one formed, but also, the formation of second phases. In addition, a very slight broadening of Bragg peaks of the perovskites sintered for 48 h is observed by XRD and can be related to the presence of two different perovskites in each sample according to EPMA results. By BSEM and EPMA analyses La{sub 4.00}Ga{sub 2.00}O{sub 9.00} (nominal composition) is also observed as second phase when samples are treated for 48 h. - Graphical abstract: Typical microstructures, observed by FEG-SEM, of La{sub 0.90}Sr{sub 0.10}Ga{sub 1−x}Ni{sub x}O{sub 3.00−δ} materials with x=0.00 and 0.10 (nominal compositions) and sintered at 1450 °C for 48 h after polishing and thermal etching are shown. Lighter grey grains with a bimodal grain size are observed and according to XEDS analysis correspond to two perovskites with different experimental compositions (labelled as 1 and 2 for x=0.00 and labelled as 4 and 5 for x=0.10, respectively), meanwhile the darker grey phases correspond to LaSrGa{sub 3.00}O{sub 7.00} (labelled as 3 for x=0.00) and LaSr(Ga{sub 1−y′},Ni{sub y′}){sub 3.00}O{sub 7.00} (labelled as 6 for x=0.10), respectively. - Highlights: • When NiO is introduced into La{sub 0.90}Sr{sub 0.10}GaO{sub 3.00−δ} a change in symmetry is produced. • A significant Sr depletion in the A-site of perovskites treated for 48 h is observed. • Compositional deviations could be due to a thermally-activated diffusional process. • The phase purity of these materials is deteriorated when the sintering time is extended.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cleaned 5-Minute Resolution Air Quality and Meteorological Data from Nine TCEQ CAMS Sites in Houston, Texas (Nov 2021 – Oct 2022)

These data encompass 5-minute air monitoring and meteorological observations collected in the greater Houston, Texas metropolitan region, at nine (9) Continuous Ambient Monitoring Stations (CAMS) operated by the Texas Commission on Environmental Quality (TCEQ) between November 1, 2021 and October 31, 2022. The CAMS sites (CAMS 1, 8, 35, 45, 148, 403, 405, 410, and 1052) were chosen because their instrumentation includes measurements of PM2.5. These sites also provide continuous multi-parameter air-quality and meteorological measurements. Particulate matter (PM2.5, PM10) was sampled along with several trace gases, including ozone (O3), nitrogen oxides (NO, NO2, NOx), sulfur dioxide (SO2), and carbon monoxide (CO). The data set also contains standard surface meteorological parameters (temperature, humidity, pressure, wind speed, and wind direction). Several sites also include AutoGC-based measurements of volatile organic compounds (VOCs). Air monitoring instruments deployed at the selected sites comprise the following systems: BAM-1020 or TEOM (PM2.5), Thermo Scientific TEI 49i (O3), TEI 42i (NOx), and AutoGCs (VOCs). This data set is similar to the data included within the houairq5mX1.00 datastream, except for a few additional quality control steps. A systematic data cleaning and verification process was performed on the data set to ensure its quality and preparation for analysis. Removal of non-numeric status flags (e.g., [LIM], [QAS], [SPZ], [CAL], [PMA], [AQI], [SPN], [MAL]) was accomplished by employing rule-based string parsing to extract valid numerical values. Missing entries were set to -9999; however, invalid or anomalous values (e.g., 99999) were retained as originally reported by the TCEQ to preserve data provenance. The time sequence was verified for completeness, removal of duplicates, and uniformity at 5-minute intervals. Column labeling was standardized, and corresponding values were assessed for physical plausibility. All timestamps in the data set were reported in Coordinated Universal Time (UTC) as provided by the TCEQ. Further, the latitude and longitude coordinates were added for each CAMS site. A subset of the data (June 1–September 30, 2022) has been used in the following publication: Subba et al. 2025. “Implications of sea breeze circulations on boundary layer aerosols in the southern coastal Texas region.” EGUsphere 2025: 1–49, https://doi.org/10.5194/egusphere-2025-2659.

latitude↗

High Flux Through the Oxidative Pentose Phosphate Pathway Lowers Efficiency in Developing Camelina Seeds

Many seeds are green during development, and light has been shown to play a role in the efficiency with which maternally supplied substrates are converted into storage compounds. However, the effects of light on the fluxes through central metabolism that determine this efficiency are poorly understood. Here, we used metabolic flux analysis to determine the effects of light on central metabolism in developing embryos of false flax (Camelina sativa). Metabolic efficiency in C. sativa is of interest because, despite its growing importance as a model oilseed and engineering target and its potential as a biofuel crop, its yields are lower than other major oilseed species. Culture conditions under which steady-state growth and composition of developing embryos match those in planta were used to quantify substrate uptake and respiration rates. The carbon conversion efficiency (CCE) was 21% 6 3% in the dark and 42% 6 4% under high light. Under physiological illumination, the CCE (32% 6 2%) was substantially lower than in green and nongreen oilseeds studied previously. 13C and 14C isotopic labeling experiments were used together with computer-aided modeling to map fluxes through central metabolism. Fluxes through the oxidative pentose phosphate pathway (OPPP) were the principal source of CO2 production and strongly negatively correlated with CCE across light levels. OPPP fluxes were greatly in excess of demand for NAD(P)H for biosynthesis and larger than those measured in other systems. Excess reductant appears to be dissipated via cyanide-insensitive respiration. OPPP enzymes therefore represent a potential target for increasing efficiency and yield in C. sativa.

09 BIOMASS FUELS↗

Litter type control on soil C and N stabilization dynamics in a temperate forest

Abstract While plant litters are the main source of soil organic matter ( SOM ) in forests, the controllers and pathways to stable SOM formation remain unclear. Here, we address how litter type ( 13 C/ 15 N‐labeled needles vs. fine roots) and placement‐depth (O vs. A horizon) affect in situ C and N dynamics in a temperate forest soil after 5 years. Litter type rather than placement‐depth controlled soil C and N retention after 5 years in situ , with belowground fine root inputs greatly enhancing soil C (x1.4) and N (x1.2) retention compared with aboveground needles. While the proportions of added needle and fine root‐derived C and N recovered into stable SOM fractions were similar, they followed different transformation pathways into stable SOM fractions: fine root transfer was slower than for needles, but proportionally more of the remaining needle‐derived C and N was transferred into stable SOM fractions. The stoichiometry of litter‐derived C vs. N within individual SOM fractions revealed the presence at least two pools of different turnover times (per SOM fraction) and emphasized the role of N‐rich compounds for long‐term persistence. Finally, a regression approach suggested that models may underestimate soil C retention from litter with fast decomposition rates.

Hatton, Pierre‐Joseph↗

Integrated research training program of excellence in radiochemistry

The overall goal of this “Integrated Research Training Program of Excellence in Radiochemistry” is to provide a rich and deep research experience in state-of-the-art radiochemistry and in the fundamentals of radioisotopic labeling and tracer methodology to develop researchers who are capable of meeting the challenges of designing and preparing radiotracers of broad applicability for monitoring and imaging diverse biological systems and environmental processes. This program was based in the Departments of Radiology and Radiation Oncology at Washington University Medical School and the Department of Chemistry at the University of Illinois at Urbana Champaign, and it was initially directed by Professor Michael J. Welch as Principal Investigator. After his passing in 2012, the program was led by Professor Suzanne E. Lapi. Programmatic content and participant progress was overseen by an Internal Advisory Committee of senior investigators consisting of the PIs, Professor Mach from the Department of Radiology at Washington University and Professor John A. Katzenellenbogen of the Department of Chemistry at the University of Illinois. A small External Advisory Committee to give overall program guidance was also constituted of experts in radiolabeled compounds and in their applications in environmental and plant science.

18F↗

High-throughput chemical imaging for optimizing biofuel synthesis using synthetic biology (Final Technical Report)

Fatty acids can be produced biosynthetically in microbes and these compounds can serve as precursors to biodiesels and other high value oleochemicals. However, progress on engineering fatty acid biosynthesis, and biofuel synthesis more generally, has been hindered by current quantification methods that are either indirect or not amenable to high-throughput or single-cell resolution screening. In this project, we assembled an interdisciplinary team with complimentary expertise in synthetic biology and microscopy, metabolic engineering, and chemical imaging to address these challenges. We used chemical imaging to directly measure lipid biosynthesis in Escherichia coli engineered to produce fatty acids, obtaining detailed single-cell resolution measurements. We deployed stimulated Raman scattering (SRS) microscopy in concert with multiplexed genome engineering and gene circuit design strategies from synthetic biology to optimize production of fatty acids. These results provided novel insight into cell-to-cell heterogeneity present in biofuel production strains. In addition, we introduced new chemical imaging methods which are label-free and do not require fluorescent reporters. These efforts were complemented by other studied developing foundational tools for regulation and control, which offer excellent potential for advancing researchers’ ability to rapidly design, build, and test strains for enhanced biofuel synthesis.

09 BIOMASS FUELS↗

Membrane-Organized Chemical Photoredox Systems

This project has three interrelated goals relevant to solar water photolysis, which are to develop: (1) vesicle-organized assemblies for H 2 photoproduction that utilize pyrylium and structurally related compounds as combined photosensitizers and cyclic electroneutral transmembrane electron carriers; (2) transmembrane redox systems whose reaction rates can be modulated by light; and (3) homogeneous catalysts for water oxidation. In area (1), initial efforts to photogenerate H 2 from vectorially-organized vesicles containing occluded colloidal Pt and commonly available pyrylium ions as transmembrane redox mediators were unsuccessful. New pyrylium compounds with significantly lower reduction potentials have been synthesized to address this problem, their apparent redox potentials in functioning systems have been now evaluated by using a series of occluded viologens, and H 2 photoproduction has been demonstrated in continuous illumination experiments. In area (2), spirooxazine-quinone dyads have been synthesized and their capacity to function as redox mediators across bilayer membranes has been evaluated through continuous photolysis and transient spectrophotometric measurements. Photoisomerization of the spiro moiety to the ring-open mero form caused net quantum yields to decrease significantly, providing a basis for photoregulation of transmembrane redox. Research on water oxidation (area 3) has been directed at understanding mechanisms of catalysis by cis,cis-[(bpy) 2 Ru(OH 2 )] 2 O 4+ and related polyimine complexes. Using a variety of physical techniques, we have: (i) identified the redox state of the complex ion that is catalytically active; (ii) shown using 18 O isotopic labeling that there are two reaction pathways, both of which involve participation of solvent H 2 O; and (iii) detected and characterized by EPR and resonance Raman spectroscopies new species which may be key intermediates in the catalytic cycle.

14 SOLAR ENERGY↗

Chamber flux measurements at US-ORv located in Columbus, OH from 2010 to 2014

Closed and flow through chamber methane and carbon dioxide flux measurements were taken at different water depths, vegetation cover types, and times of day at the Wilma H. Schiermeier Olentangy River Wetland Research Park (ORWRP) from 2010 to 2014 to investigate the effects of these variables on gas exchange. The ORWRP consists of two urban experimental wetland basins constructed in 1994 within the footprint of the AmeriFlux tower US-ORv that was functional from 2011 to 2016. Chamber measurements are separated into flow through and closed chamber files (flow_through.csv, closed_chamber.csv) with location labels corresponding with coordinates listed in the metadata file (Location_ID.csv). All files are .csv and could be viewed or analyzed with Excel, MATLAB, Python, or R.

EARTH SCIENCE > ATMOSPHERE > ATMOSPHERIC CHEMISTRY↗