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Bacterial heme nitric oxide/oxygen (H-NOX) domains are nitric oxide (NO) or oxygen sensors. This activity is mediated through binding of the ligand to a heme cofactor. However, H-NOX from Vibrio cholerae (Vc H-NOX) can be easily purified in a heme-free state that is capable of reversibly responding to oxidation, suggesting a heme-independent function as a redox sensor. This occurs by oxidation of Cys residues at a zinc-binding site conserved in a subset of H-NOX homologs. Remarkably, zinc is not lost from the protein upon oxidation, although its ligation environment is significantly altered. Using a combination of computational and experimental approaches, we have characterized localized structural changes that accompany the formation of specific disulfide bonds between Cys residues upon oxidation. Furthermore, the larger-scale structural changes accompanying oxidation appear to mimic those changes observed upon NO binding to the heme-bound form. Thus, Vc H-NOX and its homologs may act as both redox and NO sensors by completely separate mechanisms.

Exquisite control of catalytic metathesis reactivity is possible through ligand‐based variation of ruthenium carbene complexes. Sterically hindered alkenes, however, remain a generally recalcitrant class of substrates for intermolecular cross‐metathesis. Allylic chalcogenides (sulfides and selenides) have emerged as “privileged” substrates that exhibit enhanced turnover rates with the commercially available second‐generation ruthenium catalyst. Increased turnover rates are advantageous when competing catalyst degradation is limiting, although specific mechanisms have not been defined. Herein, we describe facile cross‐metathesis of allylic sulfone reagents with sterically hindered isoprenoid alkene substrates. Furthermore, we demonstrate the first example of intermolecular cross‐metathesis of ruthenium carbenes with a tetrasubstituted alkene. Computational analysis by combined coupled cluster/DFT calculations exposes a favorable energetic profile for metallacyclobutane formation from chelating ruthenium β‐chalcogenide carbene intermediates. These results establish allylic sulfones as privileged reagents for a substrate‐based strategy of cross‐metathesis derivatization.

Increasing food waste generation (1.6 billion tons per year globally) due to urban and industrial development has prompted researchers to pursue alternative waste management methods. Energy valorization of food waste is a method that can reduce the environmental impacts of landfills and the global reliance on crude oil for liquid fuels. In this study, food waste was converted to bio-crude oilviahydrothermal liquefaction (HTL) in a batch reactor at moderate temperatures (240–295°C), reaction times (0–60 min), and 15 wt.% solids loading. The maximum HTL bio-crude oil yield (27.5 wt.%), and energy recovery (49%) were obtained at 240°C and 30 min, while the highest bio-crude oil energy content (40.2 MJ/kg) was observed at 295°C. The properties of the bio-crude oil were determined using thermogravimetric analysis, fatty acid methyl ester (FAME) analysis by gas chromatography with flame ionization detection, CHNS elemental analysis, and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). FT-ICR MS results indicated that the majority of the detected compounds in the bio-crude oil were oxygen-containing species. The O4class was the most abundant class of heteroatom-containing compounds in all HTL bio-crude oil samples produced at 240°C; the O2class was the most abundant class obtained at 265 and 295°C. The total FAME content of the bio-crude oil was 15–37 wt.%, of which the most abundant were palmitic acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), and polyunsaturated fatty acids (C18:3N:3, C18:3N:6).

Guayule (Parthenium argentatum), a shrub native to the arid region of the U.S. southwest and Mexico belonging to the Asteraceae family, is a source of high quality, hypoallergenic natural rubber with applications in pharmaceutical, tire, and food industries. Production of rubber results in a substantial amount of resin-containing residues which contain a wide variety of secondary metabolites (sesquiterpene esters, triterpene alcohols, fatty acids, etc.). In order to enhance the economic viability of guayule as an industrial crop, value-added use of the residues is needed and has the potential to reduce gross rubber production costs. The main objective of this research is the characterization of guayule resin using rapid and accurate analytical techniques to identify compounds of potential commercial value. Guayule resin is inherently complex and includes many high-molecular-weight and non-volatile compounds that are not easy to observe using traditional chromatographic techniques. The combination of two mass spectroscopy techniques: gas chromatography mass spectroscopy (GC–MS) and high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS), were used to characterize the composition of the extracted resin from guayule (Parthenium argentatum). FT-ICR MS was used to characterize hundreds of compounds with over a wide range of molecular weights and degrees of aromaticity at higher levels of mass accuracy than other forms of mass spectrometry. GC–MS was used to identify volatile compounds like mono- and sesquiterpene compounds.

Bulk property measurement, simulated distillation, gas chromatography mass spectrometry (GC-MS), and ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) are utilized for direct description and comparison of the chemical composition of raw and hydrotreated biocrude samples from pine, microalgae (Chlorella sp.), and sewage sludge. With hydrotreatment, the nitrogen, oxygen, and sulfur content as well as viscosity, density, and moisture content of all biocrudes decreased to yield a more desirable product. For upgraded biocrudes, simulated distillation and GC-MS data reveal that the microalgae and sewage sludge products comprise a high proportion of n-alkanes, which distill between 260 and 350 °C, whereas the pine hydrotreated biocrude product has a lower concentration of n-alkanes and is more compositionally diverse with an abundance of saturated cyclic compounds. FT-ICR MS analysis of the raw biocrudes showed predominantly Ox species, whereas raw microalgae and sewag...

Metabolic response to four suboptimal cultivation temperatures was explored in Nannochloropsis salina, with an emphasis on fatty acid and lipid metabolism. Cultures were cultivated in controlled environmental photobioreactors. Physiological performance, characterized by growth rate and photosynthetic output, were reduced at all three cold stress temperatures (5 °C, 10 °C, 15 °C). However, biomass productivity and overall growth for cultures at 20 °C was like that of those grown at the optimal temperature (25 °C). Fatty acid productivity was elevated at all suboptimal temperatures, and both total fatty acid and eicosapentaenoic acid content were statically elevated at 20 °C. Lipid accumulation was observed exclusively in response to cold stress; however, lipid turnover and enrichment in polyunsaturated fatty acids occurred in all temperature variants. In addition, extensive lipid remodeling occurred in both polar and neutral lipid pools, specifically in monogalactosyl diacylglycerol and triacylglycerol pools. While 20 °C is optimal for eicosapentaenoic acid and total fatty acid productivity, cold stress is necessary to induce both productivity and polyunsaturated fatty acid enrichment in triacylglycerol pools.

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is utilized for direct comparison of the chemical composition of biocrudes generated from the hydrothermal liquefaction of 100% pine, 100% algae, 75:25 pine:algae, and 50:50 pine:algae feedstocks. This analysis reveals that the composition of the 72:25 and 50:50 pine:algal HTL biocrudes is essentially a composite of the two parent feeds (i.e., pine and algae) with a lower relative abundance of Ox species and a higher relative abundance of nitrogen-containing species than the pine HTL biocrude. Alternatively, the biocrude blends have a lower relative abundance of nitrogen-containing species where N > 2 than the algal HTL biocrude. The 75:25 pine:algal HTL biocrude has more elemental formulae in common with the pine HTL biocrude than the 50:50 blend; however, both blends have more elemental formulae in common with the algal HTL biocrude. Interestingly, >20% of the elemental formulae assigned to monoisotopic peaks within the 75:25 and 50:50 biocrude blends are species not present in either the pine or algal HTL biocrudes. The highest relative abundance of these new species belong to the N2O4-6 classes, which correspond to heteroatom classes with a moderate number of nitrogen atoms and higher number of oxygen atoms per molecules than the species within the pure algal HTL biocrude. Compositionally, the novel species have the same structural motif but are of higher DBE and carbon numbers than the species within the algal HTL biocrude. These original species are most likely generated from reactions between molecules from both feeds, which results in compounds with higher oxygen content than typically seen in the algal HTL biocrude but also higher nitrogen contents than observed in the pine HTL biocrude.

Hydrothermal liquefaction (HTL) of wastewater microalgae is constrained by the high ash content in the biomass. High ash content causes slagging, fouling, and catalyst deactivation. In this study, batch experiments for hydrothermal liquefaction (HTL) of filamentous algae were carried out in a 1.8-L autoclave reactor to measure the effects of reaction conditions and demineralization on the yields and quality of the products. Nitric acid was the most efficient demineralization acid, halving ash content (27.1 to 13.5 wt%). HTL of untreated algae showed that, as temperature increased from 310 to 350 °C, total bio-crude oil (light + heavy) yield slightly increased (25.4 to 28.0 wt%, dry ash-free). HTL of demineralized algae gave higher total bio-crude oil yields (27.2 to 43.4 wt%, dry ash-free), greater energy recovery (29.5 to 50.9%), higher char yields (22.1 to 32.5 wt%, dry ash-free), and decreased energy consumption ratios (from 1.0 to 0.6) compared to HTL of untreated algae. Fourier transform infrared spectroscopy (FT-IR) of the feedstocks revealed slightly higher carbohydrate content in the acid-treated biomass compared to the untreated biomass. Both FT-IR and FT ion cyclotron resonance mass spectroscopy of the bio-crude oils showed no significant difference in the functional groups and heteroatoms in the hexane-soluble bio-crude oil derived from untreated and acid-treated biomass. These results demonstrate that demineralization of wastewater algae is relevant for improving the feasibility of algal wastewater-treatment-to-biofuel systems.

The bio-crude oil produced from hydrothermal liquefaction (HTL) of a high-protein microalgae useful for wastewater treatment, Galdieria sulphuraria, was comprehensively characterized, and compared to that of a high-lipid microalgae useful for biofuel production, Nannochloropsis salina. HTL was conducted in a batch reactor at temperatures of 310–350 °C and reaction times of 5–60 min. Characterization methods included high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS), fatty acid methyl ester (FAME) analysis by gas chromatography mass spectroscopy (GC/MS), proton nuclear magnetic resonance spectroscopy (1H NMR), and Fourier transform infrared spectroscopy (FT-IR). Milder reaction conditions favored bio-crude oil yield and quality for N. salina, while more severe conditions (350 °C) were needed for G. sulphuraria. N. salina-derived bio-crude oil contained mainly C14-C18 fatty acid amides, while G. sulphuraria-derived bio-crude-oil had many N1-3O0-2 hetero-atom compounds. FT-ICR MS showed that the aromaticity of hetero-compounds in N. salina bio-crude oil was higher due to N. salina’s higher carbohydrate content and the tendency of carbohydrate-derived molecules to condense at HTL conditions. FAME-GC/MS and 1H-NMR results showed that stable fatty acid amides increased in G. sulphuraria bio-crude oil at higher temperatures as more protein-derived compounds combined with lipid-derived compounds. While N-containing and high molecular weight compounds are a concern for the upgrading of bio-crude oils obtained from high-protein algal biomass, removal of carbohydrates rather than removal of proteins as a pretreatment to HTL is recommended since carbohydrate-derived compounds are more likely to create highly aromatic hetero-compounds that are much more difficult to upgrade.

We provide a direct and detailed comparison of the chemical composition of petroleum crude oil (from the Gulf of Mexico), shale oil, and three biocrudes (i.e., clean pine, microalgae Chlorella sp., and sewage sludge feedstocks) generated by hydrothermal liquefaction (HTL). Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that HTL biocrudes are compositionally more similar to shale oil than petroleum crude oil and that only a few heteroatom classes (e.g., N1, N2, N1O1, and O1) are common to organic sediment- and biomass-derived oils. All HTL biocrudes contain a diverse range of oxygen-containing compounds when compared to either petroleum crude or shale oil. Overall, petroleum crude and shale oil are compositionally dissimilar to HTL oils, and >85% of the elemental compositions identified within the positive-ion electrospray (ESI) mass spectra of the HTL biocrudes were not present in either the petroleum crude or shale oil (>43% for negative-ion ESI). Dir...

Petroleum emulsion interfacial material (species that reside in the water/oil interface) are believed to be responsible for stabilizing emulsions in petroleum; therefore, their characterization can help to develop strategies to mitigate/manipulate petroleum emulsions. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has shown that the species present at the oil/water interface are enriched in sulfur- and oxygen-containing functionalities. However, structural and isomeric information about the chemical functionalities is still uncertain. Here, we demonstrate the potential of ion mobility mass spectrometry (IM-MS) combined with post-ion mobility collision-induced dissociation (post-IM CID) to characterize functional isomers in petroleum emulsion interfacial material. Interfacial material was isolated from Athabasca bitumen and a heavy crude oil by the wet silica method. IM time-of-flight (TOF) MS analysis shows the presence of multiple isomeric O3S1 species in both samples. Post-IM CI...

To explore the feasibility of scaling up hydrothermal liquefaction (HTL) of algal biomass, a pilot-scale continuous flow reactor (CFR) was operated to produce bio-crude oil from algal biomass cultivated in urban wastewater. The CFR system ran algal slurry (5 wt.% solids loading) at 350 °C and 17 MPa for 4 h without any clogging issues. Bio-crude oil chemistry was characterized by high-resolution Fourier transform mass spectroscopy (FT-MS), proton nuclear magnetic resonance spectroscopy (1H NMR), bomb calorimetry, and elemental analysis. Bio-crude oil yield of 28.1 wt% was obtained with higher heating values of 38–39 MJ/kg. The quality of light bio-crude oil produced from the CFR system was comparable in terms of molecular structures to bio-crude oil produced in a batch reactor.

A coupled algal-osmosis membrane treatment system was studied for recovering potable-quality water from municipal primary effluent. The core components of the system included a mixotrophic algal process for removal of biochemical oxygen demand (BOD) and nutrients, followed by a hybrid forward osmosis (FO)-reverse osmosis (RO) system for separation of biomass from the algal effluent and production of potable-quality water. Field experiments demonstrated consistent performance of the algal system to meet surface discharge standards for BOD and nutrients within a fed-batch processing time of 2–3 days. The hybrid FO-RO system reached water productivity of 1.57 L/m2-h in FO using seawater as draw solution; and permeate flux of 3.50 L/m2-h in brackish water RO (BWRO) and 2.07 L/m2-h in seawater RO (SWRO) at 2068 KPa. The coupled algal-membrane system achieved complete removal of ammonia, fluoride, and phosphate; over 90% removal of calcium, sulfate, and organic carbon; and 86–89% removal of potassium and magnesium. Broadband characterization using high resolution mass spectrometry revealed extensive removal of organic compounds, particularly wastewater surfactants upon algal treatment. This study demonstrated long-term performance of the FO system at water recovery of 90% and with membrane cleaning by NaOH solution.

Two strains of Galdieria sulphuraria algae, 5587.1 and SOOS, were grown on municipal wastewater to develop energy-positive treatment systems. Hydrothermal liquefaction (HTL) of 5–10 wt% algal biomass solids was conducted at 310–350 °C for 5–60 min to produce bio-crude oil. HTL product yields and energy recovery were compared to those from previous studies using G. sulphuraria grown on a modified Cyanidium medium. Total bio-crude oil yields were lower (11.2–23.0 wt%) and char yields were higher (22.6–36.4 wt%) for HTL of algae grown on actual wastewater compared with that grown on media (31.4 wt% and 4.8 wt%, respectively), indicating a potential limitation for using yields from media-based studies. High-resolution mass spectroscopy of bio-crude oil provides new insights into differences in composition based on growth media. Energy recovery in total bio-crude oil and char at 350 °C was 17–28% and 14–19%, respectively, for the 5587.1 strain, and 23–27% and 14–25%, respectively, for the SOOS strain.

International audience; This study investigated the adsorption and photocatalytic activity of titanium dioxide (TiO2)-boron nitride (BN) nanocomposites for the removal of contaminants of emerging concern in water using ibuprofen as a model compound. TiO2 nanofibers wrapped by BN nanosheets were synthesized by electrospinning method. Characterization of the nanocomposite photocatalysts indicated that the BN nanosheets improved the light absorbance and reduced the recombination of the photoexcited charge carriers (e(-) and h(+)). The photocatalytic oxidation products and mechanisms of ibuprofen by the TiO2-BN catalysts were elucidated using a multiple analysis approach by high performance liquid chromatography, ultraviolet absorbance, dissolved organic carbon, fluorescence excitation-emission matrices, and electrospray ionization-liquid chromatography-tandem mass spectrometry. The experimental results revealed that the photocatalytic oxidation by the TiO2-BN nanocomposites is a multi-step process and the interactions between ibuprofen molecules and the TiO2-BN nanocomposites govern the adsorption process. The increasing BN nanosheet content in the TiO2 nanofibers facilitated the breakdown of ibuprofen degradation intermediates (hydroxyibuprofen, carboxyibuprofen, and oxypropyl ibuprofen). Kinetic modeling indicated both adsorption and photocatalytic oxidation of ibuprofen by the TiO2-BN nanocomposites followed the first-order kinetic model. The photocatalytic oxidation rate increased with the increasing BN content in the nanocomposite catalysts, which was attributed to the enhanced light absorption capacity and the separation efficiency of the photoexcited electron (e(-))-hole (h(+)) pairs. Multiple photocatalytic cycles were conducted to investigate the reusability and regeneration of the nanofibers for ibuprofen degradation.

We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The iron porphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICP-OES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe = 100,728 ppm) and cyanobacteria (Fe = 115,450 ppm). Direct infusion FT-ICR MS analysis of the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron porphyrin compounds in the two HTL biocrudes that have similar carbon number and double bond equivalent distributions to the metal porphyrins (e.g. Ni and V) reported for petroleum. No iron porphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron porphyrin structures in the HTL biocrude are degraded during hydrotreatment. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.

We investigated nonisothermal (fast) and nominally isothermal hydrothermal liquefaction (HTL) of Nannochloropsis sp. microalgae for the production of biocrude. Biocrude yields ranged from 36 to 45 wt % (dry weight), with fast HTL with low mass loading giving the highest yield. This condition also gave the biocrude with the lowest heating value, which indicates there are compromises to be made between biocrude quantity and quality. The aqueous phase and biocrude product fractions were characterized using elemental analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This detailed level of analysis identified more than 30,000 unique molecular products. The aqueous phase products included compounds with the same molecular formulae as known herbicides, which may inform efforts in genetic engineering of algae and/or bacteria for cultivation on the aqueous phase. This detailed molecular-level characterization provides some clues regarding the types of reactions that may take place during HTL. © 2016 American Institute of Chemical Engineers AIChE J, 62: 815–828, 2016

In the processing of guayule (Parthenium argentatum) for bulk rubber production using solvent extraction, two residue streams are produced: a complex resin-rich liquid and a ground, dry woody bagasse. In order to enhance the economic viability of guayule as an industrial crop, value-added use of the residues is needed and has the potential to reduce gross rubber production costs. The main objective of this research is the characterization of these two residues using analytical techniques to identify potential value-added components and applications. Here, guayule bagasse and resin were characterized by CNHS/O elemental analysis, bomb calorimetry, thermogravimetric analysis, Fourier-transform infrared spectrometry (FT-IR), X-ray diffractometry (XRD), gas chromatography–mass spectrometry (GC–MS), and high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). Guayule bagasse has high energy content (22–24 MJ/kg), less moisture (0.5–1.5 wt.%) and ash (3.7–4.1 wt.%), low cellulose crystallinity (29–34 %), and abundant carbohydrates (36–38 wt.%) and lignin (22–23 wt.%) relative to plenty of other lignocellulosic biomass, indicating bagasse’s potential for thermochemical conversion to fuels. By FT-ICR MS with negative ionization mode, the most abundant classes among the 7200 heteroatom-containing compounds detected in guayule resin were O3, followed by O4 and O2. Identified compounds included fatty acids, steroids, triterpenoids, and sesquiterpene esters, some of which have never been reported, as potential precursors of industrial chemicals. Characterization of guayule bagasse and resin guides exploring potential applications of waste streams, beneficial for enhancing techno-economic feasibility of guayule rubber-derived tires manufacturing industry.

Valorization of algal biomass is often limited by its low lipid content. Here, different alcohols: ethanol, isopropanol, and glycerol, were studied as co-solvents to improve the conversion efficiency of a lipid-poor microalgae, Galdieria sulphuraria, by hydrothermal liquefaction. Bio-crude oil yield increases, from 13 to 73 wt% (on dry algae basis), were attributed to the alcohols facilitating the transfer of algal protein-derived fragments from the aqueous phase into the oil phase. A series of characterization results showed that bio-crude oil formation was mainly the result of alcohols reacting with algal fragments via Maillard reactions, alkylation, and esterification, respectively. Insights into the synergistic effect of low-lipid feed and alcohol provide mechanistic support for choosing an alcohol-rich waste, crude glycerol, to improve bio-crude oil production from HTL of wastewater-grown G. sulphuraria. Promising improvements in yield and energy recovery indicates competitive economics for a low-lipid biomass waste-to-biofuel conversion technique.

Isolation of crude oil components that concentrate at the oil/water interface [i.e., interfacial material (IM)] facilitates their molecular identification and quantitation, which is critical for advances in optimal petroleum production and processing. For a given crude oil, the molecular composition of IM determines its emulsion stability and identifies those chemistries that disproportionately contribute to the interfacial layer. Here, we describe a scalable, simple, quick, and efficient procedure to isolate IM from petroleum crude oils and/or other organic matrices. Hydrated silica (∼26 monolayers of water on a silica surface) enables separation of interfacially active species through their interaction with the immobilized water. Species with little or no interaction with the hydrated silica (water-laden) surface are eluted with a 1:1 (vol) mixture of heptane/toluene (heptol). The interfacially active species are subsequently isolated through the addition of methanol to the eluting solvent mixture, whic...

Woody biomass has the potential to be utilized at an alternative fuel source through its pyrolytic conversion. Here, fast pyrolysis bio-oils derived from several western USA woody species are characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine molecular-level composition. The composition and properties (pH, electrical conductivity, and elemental analyses) of the biochar byproduct were also determined. The bio-oils are comprised mainly of Ox species. Oak (Quercus garryana Douglas ex Hook), mixed conifer (Pseudotsuga menziesii Mirb. Franco, Tsuga heterophylla (Raf.) Sarg, Abies concolor (Gord. & Glend.) Lindl. ex Hildebr.), and scotch broom (Cytisus scoparius (L.) Link) bio-oils contain lower Ox (O1-O7) species that exhibit bimodal distributions whereas mixed conifer feedstock from a fire salvage harvest contains a larger range of Ox species (O2-O13) that exhibit a mainly monomodal distribution. Boron-containing species in the pyrolysis oils were also identified for the first time by FT-ICR MS. Biochar analysis revealed that all biochars had similar pH values (~7-8); however, the electrical conductivity and elemental analyses varied across the samples. Understanding the composition of pyrolysis byproducts will help direct their uses to the most appropriate locations.

Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150-1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed.

An alternative method to extract, quantify, and characterize water-soluble organic (WSO) species in produced water from steam-assisted gravity drainage (SAGD) is evaluated by various techniques. He...

Pyrolysis of solid biomass, in this case pine pellets and peanut hulls, generates a hydrocarbon-rich liquid product (bio-oil) consisting of oily and aqueous phases. Here, each phase is characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to yield unique elemental compositions for thousands of compounds. Bio-oils are dominated by Ox species: few oxygens per molecule for the oily phase and many more oxygens per molecules for the aqueous phase. Thus, the increased oxygen content per molecule accounts for its water solubility. Peanut hull bio-oil is much more compositionally complex and contains more nitrogen-containing compounds than pine pellet bio-oil. Bulk C, H, N, O, and S measurements confirm the increased levels of nitrogen-containing species identified in the peanut hull pyrolysis oil by FT-ICR MS. The ability of FT-ICR MS to identify and assign unique elemental compositions to compositionally complex bio-oils based on ultrah...

In humans, dietary polyunsaturated fatty acids (PUFAs) are involved in therapeutic processes such as prevention and treatment of cardiovascular diseases, neuropsychiatric disorders, and dementia. We examined the physiology, PUFA accumulation and glycerol lipid biosynthesis in the marine microalga Nannochloropsis salina in response to constant suboptimal temperature (&lt, 20 &deg, C). As expected, N. salina exhibited significantly reduced growth rate and photosynthetic activity compared to optimal cultivation temperature. Total fatty acid contents were not significantly elevated at reduced temperatures. Cultures grown at 5 &deg, C had the highest quantity of eicosapentanoic acid (EPA) (C20:5n3) and the lowest growth rate. Additionally, we monitored broadband lipid composition to model the occurrence of metabolic alteration and remodeling for various lipid pools. We focused on triacylglycerol (TAG) with elevated PUFA content. TAGs with EPA at all three acyl positions were higher at a cultivation temperature of 15 &deg, C. Furthermore, monogalactosyldiacylglycerol and digalactosyldiacylglycerol, which are polar lipids associated with chloroplast membranes, decreased with reduced cultivation temperatures. Moreover, gene expression analysis of key genes involved in Kennedy pathway for de novo TAG biosynthesis revealed bimodal variations in transcript level amongst the temperature treatments. Collectively, these results show that Nannochloropsis salina is a promising source of PUFA containing lipids.