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At least 883 records · Page 49

Thermally reconfigurable Janus droplets with nematic liquid crystalline and isotropic perfluorocarbon oil compartments

We report that mixtures of perfluorocarbon oils and hydrocarbon mesogens can be used to prepare multi-compartment (Janus) emulsion drops comprising coexisting nematic liquid crystalline (LC) and isotropic oil phases. The droplets exhibit stable spherical shapes with internal Janus-type morphologies that can be tuned widely through changes in temperature or adsorbates. In particular, we observe evidence of preferential adsorption of hydrocarbon or fluorocarbon surfactants on the interfaces of nematic versus isotropic domains, respectively, providing added control over the droplet structure. Comparisons of experiments and numerical simulations using a Landau–de Gennes continuum model provide insight into the relative importance of the LC elasticity and orientational-dependent interfacial energies on droplet morphologies and properties. Here, we show that the hierarchical organization of the LC compartments generates optical properties and responsiveness not found in emulsions of isotropic oils.

42 ENGINEERING↗

Fe{sub 3}O{sub 4}/Zeolite nanocomposites synthesized by microwave assisted coprecipitation and its performance in reducing viscosity of heavy oil

Fe{sub 3}O{sub 4}/Zeolite nanocomposites have been synthesized via microwave assisted coprecipitation method and show to be efficient in reducing viscosity of heavy oil compared to other Fe{sub 3}O{sub 4}/Zeolite nanocomposites prepared by conventional method. The following precursors such as FeCl{sub 3}⋅6H{sub 2}O, FeSO{sub 4}⋅7H{sub 2}O, NH{sub 4}OH, and natural zeolite of heulandite type were used in the sample preparation. In this study, the effect of Fe{sub 3}O{sub 4} composition in the composite and microwave time heating were investigated. Fe{sub 3}O{sub 4}/Zeolite nanocomposites were then characterized to study the influence on crystal structures, morphology and physicochemical properties. The characterization techniques include X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen physisorption. The results show that by increasing the microwave heating time, the degree of nanocomposite intergrowth can be enhanced. The nanocomposite was tested in catalytic aquathermolysis of heavy oil at 200°C for 6 h and the Fe{sub 3}O{sub 4}/zeolite of 1 to 4 ratios performed the highest viscosity reduction of heavy oil reaching 92%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Air-stable droplet interface bilayers on oil-infused surfaces

Droplet interface bilayers (DIBs) are versatile model membranes useful for synthetic biology and biosensing; however, to date they have always been confined to fluid reservoirs. Here, we demonstrate that when two or more water droplets collide on an oil-infused substrate, they exhibit non-coalescence due to the formation of a thin oil film that gets squeezed between the droplets from the bottom-up. We show that when phospholipids are included in the water droplets, a stable droplet interface bilayer forms between the non-coalescing water droplets. As with traditional oil-submerged DIBs, we were able to characterize ion channel transport by incorporating peptides into each droplet. Our findings reveal that droplet interface bilayers can function in air environments, which could potentially enable biosensing of atmospheric particulates.

Boreyko, Jonathan B↗

Reply to Delmont and Eren: Strain variants and population structure during the Deepwater Horizon oil spill

A laboratory simulation revealed the succession patterns of oil degradation and microbial community changes during the Deepwater Horizon oil spill, one of the largest environmental catastrophes in human history. Hu et al. successfully recovered genomes of several oil-degrading bacteria, including one of “Candidatus Bermanella macondoprimitus,” with high identity to the dominant Oceanospirillales 16S rRNA gene sequences recovered from the deep-ocean hydrocarbon plumes. Delmont and Eren (3) reanalyzed metagenomic data generated from these plumes to argue that this Bermanella was not present.

54 ENVIRONMENTAL SCIENCES↗

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2 . Microbial community change in these subsurface sites may affect injectivity of CO 2 , permanence of stored CO 2 , and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%, and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2 -exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2 -selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2 -exposed environments.

54 ENVIRONMENTAL SCIENCES↗

Non-conventional pathways enable pennycress (Thlaspi arvense L.) embryos to achieve high efficiency of oil biosynthesis

Abstract Pennycress (Thlaspi arvense L.) accumulates oil up to 35% of the total seed biomass, and its overall fatty acid composition is suitable for aviation fuel. However, for this plant to become economically viable, its oil production needs to be improved. In vivo culture conditions that resemble the development of pennycress embryos in planta were developed based on the composition of the liquid endosperm. Then, substrate uptake rates and biomass accumulation were measured from cultured pennycress embryos, revealing a biosynthetic efficiency of 93%, which is one of the highest in comparison with other oilseeds to date. Additionally, the ratio of carbon in oil to CO2 indicated that non-conventional pathways are likely to be responsible for such a high carbon conversion efficiency. To identify the reactions enabling this phenomenon, parallel labeling experiments with 13C-labeled substrates were conducted in pennycress embryos. The main findings of these labeling experiments include: (i) the occurrence of the oxidative reactions of the pentose phosphate pathway in the cytosol; (ii) the reversibility of isocitrate dehydrogenase; (iii) the operation of the plastidic NADP-dependent malic enzyme; and (iv) the refixation of CO2 by Rubisco. These reactions are key providers of carbon and reductant for fatty acid synthesis and elongation.

13C-labeling↗

Metabolite fingerprinting of pennycress ( Thlaspi arvense L.) embryos to assess active pathways during oil synthesis

Pennycress ( Thlaspi arvense L.), a plant naturalized to North America, accumulates high levels of erucic acid in its seeds, which makes it a promising biodiesel and industrial crop. The main carbon sinks in pennycress embryos were found to be proteins, fatty acids, and cell wall, which respectively represented 38.5, 33.2, and 27.0% of the biomass at 21 days after pollination. Erucic acid reached a maximum of 36% of the total fatty acids. Together these results indicate that total oil and erucic acid contents could be increased to boost the economic competitiveness of this crop. Understanding the biochemical basis of oil synthesis in pennycress embryos is therefore timely and relevant to guide future breeding and/or metabolic engineering efforts. For this purpose, a combination of metabolomics approaches was conducted to assess the active biochemical pathways during oil synthesis. First, gas chromatography-mass spectrometry (GC-MS) profiling of intracellular metabolites highlighted three main families of compounds: organic acids, amino acids, and sugars/sugar alcohols. Secondly, these intermediates were quantified in developing pennycress embryos by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in multiple reaction monitoring mode. Finally, partitional clustering analysis grouped the intracellular metabolites that shared a similar pattern of accumulation over time into eight clusters. In conclusion, this study underlined that: (i) sucrose might be stored rather than cleaved into hexoses; (ii) glucose and glutamine would be the main sources of carbon and nitrogen, respectively; and (iii) glycolysis, the oxidative pentose phosphate pathway, the tricarboxylic acid cycle, and the Calvin cycle were active in developing pennycress embryos.

59 BASIC BIOLOGICAL SCIENCES↗

Wettability Alteration and Enhanced Oil Recovery Induced by Proximal Adsorption of Na+, Cl – , Ca 2+ , Mg 2+ , and SO 4 2– Ions on Calcite

The underlying wettability alteration mechanism responsible for enhanced oil recovery (EOR) in carbonate reservoirs is a long-standing issue for which no consensus has yet been reached. In this paper, we report extensive quantum molecular dynamics simulations to reveal the roles of wettability modifiers Na + , Cl – , Ca 2+ , Mg 2+ , and SO 4 2– ions in EOR. Characterizing wettability by contact angle using the work-of-adhesion approach, we find that the calcite surface is strongly hydrophilic, with the first two wetting layers hindering all ions from reaching the surface, i.e., ions are only “proximally adsorbed.” Na + and Cl – ions settle closer to the surface and actually disturb the interfacial water structure of the first two wetting layers, which renders the surface less water-wet and thus inhibits oil recovery, as observed. Ca 2+ , Mg 2+ and SO 4 2– ions, on the other hand, settle farther from the surface and retain the interfacial water structure, but render the surface more water-wet by modifying the effective charge on the surface, which enhances oil recovery, as observed. The impact of the ions is more pronounced at high temperatures as proximal adsorption is enhanced. In addition to theory, we report new core flooding measurements that corroborate the theoretical results. We report the present study brings new insights into the wettability alteration mechanism in EOR at the atomic scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale structure of the oil-water interface

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. As a result, the XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

36 MATERIALS SCIENCE↗

Chemical Sensing Strategies for Real-Time Monitoring of Transformer Oil: A Review

Power transformers are a central component in the field of energy distribution and transmission. The early recognition of incipient faults in operating transformers is substantially cost effective by lessening impromptu blackouts. A standout amongst the most responsive and dependable strategies utilized for assessing the health of oil filled electrical equipment is dissolved gas analysis (DGA). Nowadays, there is an expanding requirement for better nonintrusive diagnostic and online monitoring tools to survey the internal state of the transformers. Chemical sensors are viewed as a key innovation for condition monitoring of transformer health, coordinating the non-invasiveness with typical sensor features, such as cost, usability, portability, and the integration with the data networks. Low-cost chemical sensors-based DGA techniques are expected to drastically augment the diagnostic abilities empowering the deployment on a broader range of oil filled power assets. The recent development involves both specific sensors designed to detect individual dissolved gas in transformer oil and non-specific sensors, operated in near ambient conditions, with the potential to be applied in a DGA system. In this paper, general background and operating guidelines of DGA are presented to address the origin of the gas formation, methods for their detection and the interpretation of the results by data analytics. The recent significant interest and advancements in chemical sensors to DGA applications are reviewed. Lastly, future research perspectives and challenges for the development of novel DGA chemical sensors are also discussed.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Toward sustainable production of value‐added bioenergy and industrial oils in oilseed and biomass feedstocks

Abstract Plant fatty acids are used for food, feed, fuel, and industrial materials. Structurally and chemically diverse fatty acids, referred to as unusual or specialized fatty acids, are found in the seed oils of diverse plant species. Many unusual fatty acids have potential use as alternative and renewable sources of biofuels and bio‐based industrial feedstocks due to their variant structures' physical or functional properties. Oils enriched in these fatty acids can increase the value of oilseed crops and provide co‐products that can be readily extracted from lignocellulosic materials in biomass crops. Here, we describe recent progress in strategies for enhancement of oil production and quality in oilseed crops and the extension of this knowledge for metabolic engineering of biomass crops. Successful implementation of these strategies, in part, through the use of emerging synthetic biology tools, will provide added product value for the economic sustainability of biomass crops as bioenergy feedstocks.

Park, Kiyoul↗

Geostatistical Mapping of Salinity Conditioned on Borehole Logs, Montebello Oil Field, California

We present a geostatistics-based stochastic salinity estimation framework for the Montebello Oil Field that capitalizes on available total dissolved solids (TDS) data from groundwater samples as well as electrical resistivity (ER) data from borehole logging. Data from TDS samples (n = 4924) was coded into an indicator framework based on falling below four selected thresholds (500, 1000, 3000, and 10,000 mg/L). Collocated TDS-ER data from the surrounding groundwater basin were then employed to produce a kernel density estimator to establish conditional probabilities for ER data (n = 8 boreholes) falling below the selected TDS thresholds within the Montebello Oil Field area. Directional variograms were estimated from these indicator coded data, and 500 TDS realizations from conditional indicator simulation were generated for the subsurface region above the Montebello Oil Field reservoir. Simulations were summarized as 3D maps of median TDS, most likely salinity class, and probability for exceeding each of the specified TDS thresholds. Results suggested TDS was below 500 mg/L in most of the study area, with a trend toward higher values (500 to 1000 mg/L) to the southwest; consistent with the average regional groundwater flow direction. Discrete localized zones of TDS greater than 1000 mg/L were observed, with one of these zones in the greater than 10,000 mg/L range; however, these areas were not prevalent. The probabilistic approach used here is adaptable and is readily modified to include additional data and types and can be employed in time-lapse salinity modeling through Bayesian updating.

54 ENVIRONMENTAL SCIENCES↗

Identification of bottlenecks in the accumulation of cyclic fatty acids in camelina seed oil

Modified fatty acids (mFA) have diverse uses, e.g., cyclopropane fatty acids (CPA) are feedstocks for producing coatings, lubricants, plastics, and cosmetics. The expression of mFA-producing enzymes in crop and model plants generally results in lower levels of mFA accumulation than in their natural-occurring source plants. In order to further our understanding of metabolic bottlenecks that limit mFA accumulation, we generated transgenic Camelina sativa lines co-expressing Escherichia coli cyclopropane synthase (EcCPS) and Sterculia foetida lysophosphatidic acid acyltransferase (SfLPAT). In contrast to transgenic CPA-accumulating Arabidopsis, CPA accumulation in camelina caused only minor changes in seed weight, germination rate, oil accumulation, and seedling development. CPA accumulated to much higher levels in membrane than storage lipids, comprising more than 60% of total fatty acid in both phosphatidylcholine (PC) and phosphatidylethanolamine (PE) versus 26% in diacylglycerol (DAG) and 12% in triacylglycerol (TAG) indicating bottlenecks in the transfer of CPA from PC to DAG and from DAG to TAG. Upon coexpression of SfLPAT with EcCPS, di-CPA-PC increased by ~50% relative to lines expressing EcCPS alone with the di-CPA-PC primarily observed in the embryonic axis and mono-CPA-PC primarily in cotyledon tissue. EcCPS-SfLPAT lines revealed a redistribution of CPA from the sn-1 to sn-2 positions within PC and PE that was associated with a doubling of CPA accumulation in both DAG and TAG. Finally, the identification of metabolic bottlenecks in acyl transfer between site of synthesis (phospholipids) and deposition in storage oils (TAGs) lays the foundation for the optimizing CPA accumulation through directed engineering of oil synthesis in target crops.

59 BASIC BIOLOGICAL SCIENCES↗

Creating yellow seed Camelina sativa with enhanced oil accumulation by CRISPR ‐mediated disruption of Transparent Testa 8

Summary Camelina ( Camelina sativa L.), a hexaploid member of the Brassicaceae family, is an emerging oilseed crop being developed to meet the increasing demand for plant oils as biofuel feedstocks. In other Brassicas, high oil content can be associated with a yellow seed phenotype, which is unknown for camelina. We sought to create yellow seed camelina using CRISPR/Cas9 technology to disrupt its Transparent Testa 8 (TT8) transcription factor genes and to evaluate the resulting seed phenotype. We identified three TT8 genes, one in each of the three camelina subgenomes, and obtained independent CsTT8 lines containing frameshift edits. Disruption of TT8 caused seed coat colour to change from brown to yellow reflecting their reduced flavonoid accumulation of up to 44%, and the loss of a well‐organized seed coat mucilage layer. Transcriptomic analysis of CsTT8 ‐edited seeds revealed significantly increased expression of the lipid‐related transcription factors LEC1 , LEC2 , FUS3 , and WRI1 and their downstream fatty acid synthesis‐related targets. These changes caused metabolic remodelling with increased fatty acid synthesis rates and corresponding increases in total fatty acid (TFA) accumulation from 32.4% to as high as 38.0% of seed weight, and TAG yield by more than 21% without significant changes in starch or protein levels compared to parental line. These data highlight the effectiveness of CRISPR in creating novel enhanced‐oil germplasm in camelina. The resulting lines may directly contribute to future net‐zero carbon energy production or be combined with other traits to produce desired lipid‐derived bioproducts at high yields.

59 BASIC BIOLOGICAL SCIENCES↗

Expression of a Bacterial Trehalose 6-Phosphate Synthase Gene otsA in Camelina sativa Seeds Promotes the Channelling of Carbon Towards Oil Accumulation

Improving seed oil yield is essential for developing Camelina sativa as a sustainable biofuel crop. Fatty acid synthesis depends on the production of acetyl-CoA from photosynthetically derived sugars. Trehalose 6-phosphate (T6P), a proxy for sucrose availability, can link sugar status to plant growth and development. Synthesised by trehalose 6-phosphate synthase (TPS) from UDP-glucose and glucose-6-phosphate, T6P plays a regulatory role in metabolism. Our previous studies on Arabidopsis transgenic lines constitutively expressing the E. coli otsA (encoding TPS) showed increased T6P levels and seed triacylglycerol, along with stunted growth. In the present study we express otsA in camelina under the control of a seed-specific Phaseolin promoter. Seeds of the resulting transgenic lines accumulated high levels of T6P, and a 15%–20% increase in total fatty acids and triacylglycerol compared to wild-type. Molecular analysis showed the transgenic seeds had reduced SnRK1 activity, elevated WRI1 protein levels, and increased the levels of WRI1 and its target genes, along with enhanced rates of fatty acid synthesis that increased seed weights relative to wild type. Notably, the increase in oil did not affect seed protein levels but did reduce the soluble metabolite fraction. Crucially, seed-specific expression of otsA mitigated the growth defects associated with constitutive otsA expression, and the transgenic lines showed normal seed development and germination. These findings demonstrate that targeted T6P modulation via seed-specific otsA expression is an effective metabolic engineering strategy to boost oil production in camelina and potentially in other oilseed crops and bioenergy crops such as energycane, sorghum and miscanthus.

59 BASIC BIOLOGICAL SCIENCES↗

Hydroformylation of pyrolysis oils to aldehydes and alcohols from polyolefin waste

Waste plastics are an abundant feedstock for the production of renewable chemicals. Pyrolysis of waste plastics produces pyrolysis oils with high concentrations of olefins (>50 weight %). The traditional petrochemical industry uses several energy-intensive steps to produce olefins from fossil feedstocks such as naphtha, natural gas, and crude oil. In this work, we demonstrate that pyrolysis oil can be used to produce aldehydes through hydroformylation, taking advantage of the olefin functionality. These aldehydes can then be reduced to mono- and dialcohols, oxidized to mono- and dicarboxylic acids, or aminated to mono- and diamines by using homogeneous and heterogeneous catalysis. This route produces high-value oxygenated chemicals from low-value postconsumer recycled polyethylene. Here, we project that the chemicals produced by this route could lower greenhouse gas emissions ~60% compared with their production through petroleum feedstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Water Microbial Community Response to the Biocide 2,2-Dibromo-3-Nitrilopropionamide, Used in Unconventional Oil and Gas Extraction

Production of unconventional oil and gas continues to rise, but the effects of high-density hydraulic fracturing (HF) activity near aquatic ecosystems are not fully understood. A commonly used biocide in HF, 2,2-dibromo-3-nitrilopropionamide (DBNPA), was studied in microcosms of HF-impacted (HF+) versus HF-unimpacted (HF-) surface water streams to (i) compare the microbial community response, (ii) investigate DBNPA degradation products based on past HF exposure, and (iii) compare the microbial community response differences and similarities between the HF biocides DBNPA and glutaraldehyde. The microbial community responded to DBNPA differently in HF-impacted versus HF-unimpacted microcosms in terms of the number of 16S rRNA gene copies quantified, alpha and beta diversity, and differential abundance analyses of microbial community composition through time. The differences in microbial community changes affected degradation dynamics. HF-impacted microbial communities were more sensitive to DBNPA, causing the biocide and by-products of the degradation to persist for longer than in HF-unimpacted microcosms. A total of 17 DBNPA by-products were detected, many of them not widely known as DBNPA by-products. Many of the brominated by-products detected that are believed to be uncharacterized may pose environmental and health impacts. Similar taxa were able to tolerate glutaraldehyde and DBNPA; however, DBNPA was not as effective for microbial control, as indicated by a smaller overall decrease of 16S rRNA gene copies/ml after exposure to the biocide, and a more diverse set of taxa was able to tolerate it. These findings suggest that past HF activity in streams can affect the microbial community response to environmental perturbation such as that caused by the biocide DBNPA. IMPORTANCE Unconventional oil and gas activity can affect pH, total organic carbon, and microbial communities in surface water, altering their ability to respond to new environmental and/or anthropogenic perturbations. These findings demonstrate that 2,2-dibromo-3-nitrilopropionamide (DBNPA), a common hydraulic fracturing (HF) biocide, affects microbial communities differently as a consequence of past HF exposure, persisting longer in HF-impacted (HF+) waters. These findings also demonstrate that DBNPA has low efficacy in environmental microbial communities regardless of HF impact. These findings are of interest, as understanding microbial responses is key for formulating remediation strategies in unconventional oil and gas (UOG)-impacted environments. Moreover, some DBNPA degradation by-products are even more toxic and recalcitrant than DBNPA itself, and this work identifies novel brominated degradation by-products formed.

59 BASIC BIOLOGICAL SCIENCES↗

Demonstration Results from Greenhouse Heating with Bio-Oil

Bio-oils from loblolly pine (Pinus taeda) and white oak (Quercus alba) wood were produced by the laboratory scale auger reactor located at the Department of Forest Products, Mississippi State University (MSU). The bio-oils were esterified to boiler fuel by a technology developed at MSU. The testing of esterified bio-oil combustion was performed at Natchez Trace Greenhouses located in Kosciusko, Mississippi. At the greenhouse facility an idled natural gas/diesel boiler was retrofit with a highly aerated fuel injection system. Fifteen gallons of loblolly pine esterified boiler fuel and 15 gallons of white oak boiler fuel were successfully combusted in the retrofit boiler.

09 BIOMASS FUELS↗