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At least 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Organochlorine pesticides and polychlorinated biphenyls in human adipose tissue from northern Tunisia: Current extent of contamination and contributions of socio-demographic characteristics and dietary habits

The aims of the present study were to investigate the current exposure levels of persistent organochlorine compounds (OCs) in adipose tissues intraoperatively collected from 40 patients over 20 years undergoing non-cancer-related surgery residing in Northern region of Tunisia (Bizerte), which constitutes an exemplary case, and examined association between levels of contamination and both socio-demographic characteristics and dietary habits. Concentration of hexachlorobenzene (HCB), hexachlorocyclohexane isomers (α-HCH, β-HCH, γ-HCH and δ-HCH), dichlorodiphenyltrichloroethane isomers (p,p′-DDT and o,p′-DDT) and metabolites (p,p′-DDE, o,p′-DDE, p,p′-DDD and o,p′-DDD) and 12 polychlorinated biphenyls (PCBs) congeners were measured using capillary gas chromatography with electron capture detector. Overall, residue levels of OCs followed the decreasing order of DDTs > PCBs > HCB > HCHs. DDTs levels ranged from 74.49 to 1834.76 ng g{sup −1} lipid and contributing to more than 90% to the sum of organochlorine pesticides (OCPs). p,p′-DDE was the most abundant in all samples and the p,p′-DDT/p,p′-DDE ratio (range between 1.85% and 58.45%) suggesting recent and ongoing exposure to banned commercial DDT products. PCB concentrations varied from 29.27 to 322.58 ng g{sup −1} lipid and PCB-180, PCB-153 and PCB-138 were the dominant congeners accounting for 70% of total PCBs. We did not find significant correlations between OC exposure levels and sex, parity, habitat areas and smoking habits. In females, the adipose tissue concentrations of DDTs, HCB and PCB-118 were positively correlated with age. There was statistically significant relationship between body mass index (BMI) changes and the adipose tissue levels of HCB and HCHs. No association was found between OCPs levels and dietary factors. However, our study suggests that fish consumption may be an important contributor of PCBs adipose tissue content of PCBs in Tunisian people. The presented work is highly significant, being the first study pointing out the chronic exposure to OCs in Bizerte. - Highlights: • First study to report HCB, HCHs, DDTs and PCBs in adipose tissues from Tunisia. • The measurement levels showed a general pattern as DDTs>PCBs> HCB>HCHs. • p,p′-DDE and PCB-180, PCB-153 and PCB-138 were the marker substances of OCPs and PCBs, respectively. • Strong associations between concentrations of OCPs and PCBs suggest Tunisian are exposed via similar routes. • Fish consumption is a major source of dietary exposure to PCBs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Urinary bisphenol A concentrations are associated with reproductive parameters in young men

Highlights: • Urinary BPA concentrations were analyzed to estimate environmental exposure. • Serum reproductive hormone levels and semen parameters were evaluated. • Negative associations between BPA and sperm counts were found. • Increasing BPA concentrations were associated with altered LH levels. • BPA exposure may adversely impact reproductive function in young men. Bisphenol A (BPA) is a pervasive environmental toxicant with known reproductive effects on sperm parameters and hormone levels. Several observational studies have investigated the associations between BPA exposure and male reproductive function, but findings are inconsistent. The objective of this study was to assess the associations between urinary BPA concentrations and semen quality and reproductive hormone levels in a cross-sectional study with 215 healthy young university students (18–23 years old), investigated between 2010 and 2011 in Southern Spain (Murcia Region). All subjects provided urine, blood serum and semen samples on a single day. Urinary BPA concentrations were measured by dispersive liquid–liquid microextraction and ultra-high performance liquid chromatography with tandem mass spectrometry detection. Semen quality was evaluated by measuring volume, concentration, motility, morphology and total sperm count (TSC). Serum samples were analyzed for reproductive hormones, including follicle-stimulating hormone (FSH), luteinizing hormone (LH), testosterone, inhibin B and estradiol. Relationships between urinary BPA concentrations and semen quality parameters and reproductive hormone levels were examined using linear regression, adjusting for potential confounders and covariates. Ninety-five percent of the men had detectable urinary BPA concentrations with unadjusted median (5th–95th) of 2.8 (0.16–11.5) ng/mL. After adjustment for important covariates, there was a significant positive association between urinary BPA concentrations and serum LH levels (β = 0.07, 95%CI: 0.02;0.12, p-value < 0.01). Urinary BPA concentration was also significantly and inversely associated with sperm concentration (β = − 0.04, 95%CI: − 0.07;− 0.02, p-value < 0.01) and TSC (β = − 0.05, 95%CI: − 0.08;− 0.02, p-value < 0.01). No significant associations were found between BPA and other semen parameters or reproductive hormone levels. Our results support the hypothesis that BPA exposure may be associated with a reduction in Leydig cell capacity (increased LH levels) and decreased sperm counts in young men.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

UV-filters and musk fragrances in seafood commercialized in Europe Union: Occurrence, risk and exposure assessment

Highlights: • Largest survey on UV-Fs and musks in seafood commercialized in Europe. • Farmed seabream showed the highest average concentration of UV-Fs. • Wild mackerel showed the highest average concentration of polycyclic musks. • UV-Fs and musks in raw samples were far below the estimated toxicological reference value. In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species – mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice – were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs – EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Metabolites of organophosphate ester flame retardants in urine from Shanghai, China

Highlights: • Nine organophosphate ester (OPE) metabolites were determined in urine from a population in Shanghai. • Urinary levels of OPE metabolites were lower than those from more developed countries. • Age of donors and age of homes were determinants of diphenyl phosphate (DPHP) and di-n-butyl phosphate (DNBP) exposures. • Urinary DNBP levels were associated with self-reported symptoms of allergy. The metabolites of nine organophosphate ester (OPE) flame retardants were measured in 180 urine samples collected from a population (including adults and children) in western Shanghai, China, using liquid chromatography-tandem spectrometry (LC-MS/MS). The total urinary concentrations of nine OPE metabolites ranged 100–23800 pg/mL, with a geometric mean (GM) value of 1450 pg/mL. The concentrations of alkyl-OPE metabolites (879 pg/mL) were approximately an order of magnitude higher than those of aryl-OPE (53.7 pg/mL) and chlorinated-OPE metabolites (52.7 pg/mL). Diphenyl phosphate (DPHP), diethyl phosphate (DEP), di-n-butyl phosphate (DNBP), bis(2-ethylhexyl) phosphate (BEHP), and bis(2-butoxyethyl) phosphate (BBOEP) were the dominant OPE metabolites found in urine. The results showed that an increase in age was associated with a significant decrease in urinary DPHP (r = −0.278, p < 0.01) and DNBP (r = −0.314, p < 0.01) concentrations. The highest concentrations of DPHP (GM = 80.7 pg/mL) and DNBP (GM = 16.9 pg/mL) were found in urine from people living in homes that were less than 10 years old. The urinary DNBP concentration was significantly associated with self-reported symptoms of allergy. Our result establishes baseline value for OPE exposure in a population in China for comparison in future studies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Occurrence and ecological risk of pharmaceuticals in river surface water of Bangladesh

Highlights: • Twelve pharmaceuticals were investigated in river surface water. • Nine pharmaceuticals were detected at ng L{sup −1} level. • MNZ was dominant followed by TMP, ERY-H{sub 2}O and SMX. • Contamination of SMX, TMP and TYL was associated with fed aquaculture. • Preliminary ecological risk assessment showed the medium to low risks. Pharmaceutical contamination in the aquatic environment is a global issue that affects aquatic animals, micro-organisms and human health. The occurrence and preliminary ecological risk of 12 (11 antibiotics and 1 antiepileptic drug) pharmaceuticals were investigated for the first time in the surface water of the old Brahmaputra River, where open-water-fed aquaculture activities are being practiced in Bangladesh. The pharmaceuticals were quantified by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS), operated with positive electrospray ionization (ESI{sup +}) and a multiple reaction monitoring (MRM) mode. Nine pharmaceuticals were detected in the river surface water, whereas three were below the limit of detection (LOD). Metronidazole was detected in all the samples with concentrations ranging from 0.05 to 13.51 ng L{sup −1}. Trimethoprim had the second highest frequency of detection (95%) with the highest concentration (17.20 ng L{sup −1}). The ranges of concentration and detection frequency of sulfonamides and macrolides were < LOD-11.35 and < LOD-16.68 ng L{sup −1}; 35–70 and 60–85%, respectively, whereas carbamazepine was in the range of < LOD-8.80 ng L{sup −1} and had a detection frequency of 65%. The concentrations of sulfamethoxazole, trimethoprim, erythromycin-H{sub 2}O and tylosin were distinctly higher in the fed aquaculture areas. The principal component analysis confirmed that fed aquaculture activities contributed most of the pharmaceutical contamination in the river surface water. Hospitals, nursing homes, sewage wastewater or surface runoff from the surrounding areas might all contribute to the presence of metronidazole and carbamazepine. The preliminary ecological risk assessment revealed that sulfamethoxazole, erythromycin-H{sub 2}O and tylosin showed medium risk, and carbamazepine displayed low risk to sensitive aquatic organisms for maximum measured concentrations. Thus, this study suggests that pharmaceutical contamination in different rivers and seasons needs to be quantified, and ecological as well as human health risks need to be assessed in Bangladesh.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Multiple-metal exposure, diet, and oxidative stress in Uruguayan school children

Highlights: • In 6–8 year-old children, we examined associations between urinary concentrations of arsenic, cadmium, and lead, and urinary F{sub 2}–8α isoprostane and 8-hydroxy-2-deoxy-guanosine (8-OHdG). • Even at low-level, each doubling in urinary arsenic concentrations was associated with ~ 10 ng/mL higher 8-OHdG concentratio. • An indicator of mixture of the three metals was associated with higher 8-OHdG concentrations. • We found no effect modification by children's dietary antioxidant intake. Oxidative stress (OS) is an important consequence of exposure to toxic metals but it is unclear to what extent low-level metal exposures contribute to OS in children. We examined the cross-sectional association between urinary concentrations of arsenic (As), cadmium (Cd), and lead (Pb) and urinary markers of OS: F{sub 2}–8α isoprostane and 8-hydroxy-2-deoxy-guanosine (8-OHdG). We also tested effect modification by dietary intakes. Of the 211 children aged 6–8 years living in Montevideo who were eligible for the study because they had at least one OS marker measured via ELISA, 143 were included in a complete-case analysis. Urinary metals were measured with inductively coupled plasma mass spectrometry (ICP-MS: Pb, Cd) and high-performance liquid chromatography online with hydride generation ICP-MS (As-metabolites); concentrations were log{sub 2}-transformed. All urinary markers were adjusted for specific gravity of urine. Two 24-h dietary recalls were conducted to estimate children's dietary intakes, including total fruit and vegetable consumption and vitamin C, zinc and fiber intake. Ordinary least square (OLS) and weighted quantile sum (WQS) regressions were used to estimate the association between metals and each OS marker as outcome. Metal exposure was generally low: median urinary As, Cd, Pb 9.6 μg/L, 0.06 μg/L and 1.9 μg/L, respectively. Median 8-isoprostane concentration was 1.1 and 8-OHdG 39.6 ng/mL. Log{sub 2}-transformed urinary As concentrations were positively associated with 8-OHdG concentrations (10.90 [3.82, 17.97]) in covariate-adjusted OLS models which also took account of exposure to Cd and Pb. In WQS, a mixture index was also associated with higher 8-OHdG (8.71 [1.12, 16.3] for each 25% increase in index value), mostly driven by As exposure. There was little evidence of effect modification by dietary antioxidants. In sum, even at low-level, As exposure is associated with detectable oxidative damage to the DNA.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Interactive effects of nonylphenol and bisphenol A exposure with oxidative stress on fetal reproductive indices

Highlights: • Maternal NP exposure may induce 8-OHdG and 8-NO{sub 2}Gua. • Prenatal BPA may induce 8-isoPF{sub 2α}. • Concurrent exposure to NP and BPA may enhance 8-OHdG. • In the high 8-isoPF{sub 2α} group, NP/BPA is inversely related with the fetal penis length. • The interactions of NP/BPA, oxidative stress and penis length should be considered. Nonylphenol (NP) and/or bisphenol A (BPA) may have reproductive effects. Although the mechanisms of action remain unclear, steroid hormones biosynthesis, hypothalamus pituitary adrenal axis activity, oxidative stress, and crosstalk interaction of NP and BPA mixture and its pathways may play a contributory role. This cross-sectional study examined whether the interactive effects of NP/BPA and oxidative stress biomarkers played a role in reproductive indices (penis length and anogenital distance (AGD)) in 244 mother-fetus pairs. Four biomarkers of oxidative stress, (8-hydroxy-2′-deoxyguanosine (8-OHdG), 8-nitroguanine (8-NO{sub 2}Gua), 8-iso-prostaglandin F{sub 2α} (8-isoPF{sub 2α}), and 4-hydroxy-2-nonenal-mercapturic acid (HNE-MA)) were simultaneously analyzed using the high-performance liquid chromatography-electrospray ionization tandem mass spectrometry method. No significant associations were found between reproductive indices and NP/BPA or oxidative stress biomarkers. Maternal exposure to a mixture of NP and BPA may enhance 8-OHdG. Interactive effects were found in the high 8-isoPF{sub 2α} group, and prenatal NP exposure was inversely associated with penis length (β = −3.68 mm; p = 0.01). Similar results were noted among boys who were born to mothers in the high 8-isoPF{sub 2α} group, in which BPA was inversely associated with penis length (β = −4.43 mm; p = 0.005). Our findings suggest important implications for prenatal exposure to oxidative stress, as evidenced by the 8-isoPF2α level. Thus, NP and BPA may interact to shape fetal reproductive tract development, particularly in boys. The interactive effects of NP/BPA, oxidative stress, and reproductive indices should be considered.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2010

Evidence for Ligand Hydrolysis and Fe(III) Reduction in the Dissolution of Goethite by Desferrioxamine-B

Desferrioxamine-B (DFOB) is a bacterial trihydroxamate siderophore and probably the most studied to date. However, the manner in which DFOB adsorbs at mineral surfaces and promotes dissolution is still under discussion. Here we investigated the adsorption and dissolution reactions in the goethite DFOB system using both in situ infrared spectroscopic and quantitative analytical methods. Experiments were carried out at a total DFOB concentration of 1 lmol/m2, at pH 6, and in the absence of visible light. Our infrared spectroscopic results indicated that the adsorption of DFOB was nearly complete after a 4-h reaction time. In an attempt to determine the coordination mode at the goethite surface, we compared the spectrum of adsorbed DFOB after a 4-h reaction time to the spectra of model aqueous species. However, this approach proved too simplistic in the case of such a complex ligand as DFOB, and we suggest that a more detailed investigation (IR in D2O, EXAFS of adsorbed model complexes) is needed to elucidate the structure of the adsorbed siderophore. Between a 4-h and 4-day reaction time, we observed the growth of carboxylate stretching bands at 1548 and 1404 cm1, which are indicators of DFOB hydrolysis. Acetate, a product of DFOB hydrolysis at its terminal hydroxamate group, was quantified by ion chromatography. Its rate of formation was linear and nearly the same as the rate of Fe(III) dissolution. The larger hydrolysis product, a hydroxylamine fragment, was not detected by LC MS. However, a signal due to the oxidized form of this fragment, a nitroso compound, was found to increase linearly with time, which is an indirect indication for Fe(III) reduction. Based on these findings, we propose that DFOB undergoes metal-enhanced hydrolysis at the mineral surface followed by the reduction of surface Fe(III). While Fe(II) was not detected in solution, this is likely because it remains adsorbed at the goethite surface or becomes buried in the goethite crystal by electron conduction. Taking into account the extent and similarity between the rates of hydrolysis and dissolution, we suggest that a reductive mechanism could play an important part in the dissolution of goethite by DFOB. This possibility has not been considered previously in the absence of light and at circumneutral pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Short Hairpin RNA Suppression of Thymidylate Synthase Produces DNA Mismatches and Results in Excellent Radiosensitization

Purpose: To determine the effect of short hairpin ribonucleic acid (shRNA)-mediated suppression of thymidylate synthase (TS) on cytotoxicity and radiosensitization and the mechanism by which these events occur. Methods and Materials: shRNA suppression of TS was compared with 5-fluoro-2 Prime -deoxyuridine (FdUrd) inactivation of TS with or without ionizing radiation in HCT116 and HT29 colon cancer cells. Cytotoxicity and radiosensitization were measured by clonogenic assay. Cell cycle effects were measured by flow cytometry. The effects of FdUrd or shRNA suppression of TS on dNTP deoxynucleotide triphosphate imbalances and consequent nucleotide misincorporations into deoxyribonucleic acid (DNA) were analyzed by high-pressure liquid chromatography and as pSP189 plasmid mutations, respectively. Results: TS shRNA produced profound ({>=}90%) and prolonged ({>=}8 days) suppression of TS in HCT116 and HT29 cells, whereas FdUrd increased TS expression. TS shRNA also produced more specific and prolonged effects on dNTPs deoxynucleotide triphosphates compared with FdUrd. TS shRNA suppression allowed accumulation of cells in S-phase, although its effects were not as long-lasting as those of FdUrd. Both treatments resulted in phosphorylation of Chk1. TS shRNA alone was less cytotoxic than FdUrd but was equally effective as FdUrd in eliciting radiosensitization (radiation enhancement ratio: TS shRNA, 1.5-1.7; FdUrd, 1.4-1.6). TS shRNA and FdUrd produced a similar increase in the number and type of pSP189 mutations. Conclusions: TS shRNA produced less cytotoxicity than FdUrd but was equally effective at radiosensitizing tumor cells. Thus, the inhibitory effect of FdUrd on TS alone is sufficient to elicit radiosensitization with FdUrd, but it only partially explains FdUrd-mediated cytotoxicity and cell cycle inhibition. The increase in DNA mismatches after TS shRNA or FdUrd supports a causal and sufficient role for the depletion of dTTP thymidine triphosphate and consequent DNA mismatches underlying radiosensitization. Importantly, shRNA suppression of TS avoids FP-mediated TS elevation and its negative prognostic role. These studies support the further exploration of TS suppression as a novel radiosensitizing strategy.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Surface energy of air fractionated corn stover

Despite decades of research, Integrated Biorefineries (IBRs) are still not commercially viable because of the long-standing, unresolved challenges related to biomass solids handling and transport (e.g., flowability and fouling), and pretreatment e.g., wettability and conversion). The compendium of challenges facing IBRs lead to operational reliability and time-on-stream estimates of 30%, yet economically viable IBRs require greater than 90% operational reliabilities. The performance of commercial solids handling operations is largely dependent on the fundamental thermodynamic property, surface energy. Combining surface area, thermogravimetric, and inverse gas chromatography analyses, we show the observed differences in surface energy (e.g., wettability and work of cohesion) for anatomically air fractionated corn ( Zea mays L.) stover. Furthermore, this study highlights the importance of understanding and tuning biomass surface energy to improve IBR solids handling and transport, and pretreatment operations.

09 BIOMASS FUELS↗
DOE OSTI2023

HPLC-Parallel accelerator and molecular mass spectrometry analysis of 14 C-labeled amino acids

Accelerator mass spectrometry (AMS) is the method of choice for quantitation of low amounts of 14 C-labeled biomolecules. Despite exquisite sensitivity, an important limitation of AMS is its inability to provide structural information about the analyte. This limitation is not critical when the labeled compounds are well-characterized prior to AMS analysis. However, analyte identity is important in other experiments where, for example, a compound is metabolized and the structures of its metabolites are not known. We previously described a moving wire interface that enables direct AMS measurement of liquid sample in the form of discrete drops or HPLC eluent without the need for individual fraction collection, termed liquid sample-AMS (LS-AMS). Here, we now report the coupling of LS-AMS with a molecular mass spectrometer, providing parallel accelerator and molecular mass spectrometry (PAMMS) detection of analytes separated by liquid chromatography. The repeatability of the method was examined by performing repeated injections of 14 C-labeled tryptophan, and relative standard deviations of the 14 C peak areas were ≤10.57% after applying a normalization factor based on a standard. Five 14 C-labeled amino acids were separated and detected to provide simultaneous quantitative AMS and structural MS data, and AMS results were compared with solid sample-AMS (SS-AMS) data using Bland-Altman plots. To demonstrate the utility of the workflow, yeast cells were grown in a medium with 14 C-labeled tryptophan. The cell extracts were analyzed by PAMMS, and 14 C was detected in tryptophan and its metabolite kynurenine.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Improved lipid analysis using a 2D-LC-MS system with a novel injection procedure

The aim of this study was to improve analysis of nonpolar lipidomics sample extracts using reversed phase (RP) chromatography. A 4/3/3 (v/v/v) mixture of methanol/methyl tert-butyl ether/chloroform (MeOH/MTBE/CHCl 3 , MMC) was chosen for sample extraction solvent based on its proven extraction capability for several lipid classes. To avoid carry over, loss of analytes and peak distortion the loops and all capillaries of the presented LC system were flushed and filled up with methanol until the analytical column. Here, the choice of methanol was due to its weak elution strength and being infinitely miscible with MMC and several other nonpolar solvents. This allowed injection of a 100 μl sample that was 20 μl nonpolar extraction solvent diluted fivefold with methanol. All lipids of 25 lipid classes were transferred quantitatively to the column head where the online dilution of methanol was carried out with aqueous eluent for focusing the lipid analytes. The weak elution strength of methanol prevented peak distortions. The consecutive reversed phase elution resulted in remarkably narrow peaks (full width at half maximum was 0.07–0.08 min typically) and enhanced sensitivity (limit of detection usually in sub nM region) because of increased sample injection volume and narrow peaks. Calibration and quality control samples made by diluting commercial lipid standards 200–50000 times confirmed the applicability of this approach both for targeted lipid quantification and for untargeted quantitative comparison of lipids from different sources.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2015

The Clp Chaperones and Proteases of the Human Malaria Parasite Plasmodium falciparum

The Clp chaperones and proteases play an important role in protein homeostasis in the cell. They are highly conserved across prokaryotes and found also in the mitochondria of eukaryotes and the chloroplasts of plants. They function mainly in the disaggregation, unfolding and degradation of native as well as misfolded proteins. Here, we provide a comprehensive analysis of the Clp chaperones and proteases in the human malaria parasite Plasmodium falciparum. The parasite contains four Clp ATPases, which we term PfClpB1, PfClpB2, PfClpC and PfClpM. One PfClpP, the proteolytic subunit, and one PfClpR, which is an inactive version of the protease, were also identified. Expression of all Clp chaperones and proteases was confirmed in blood-stage parasites. The proteins were localized to the apicoplast, a non-photosynthetic organelle that accommodates several important metabolic pathways in P. falciparum, with the exception of PfClpB2 (also known as Hsp101), which was found in the parasitophorous vacuole. Both PfClpP and PfClpR form mostly homoheptameric rings as observed by size-exclusion chromatography, analytical ultracentrifugation and electron microscopy. The X-ray structure of PfClpP showed the protein as a compacted tetradecamer similar to that observed for Streptococcus pneumoniae and Mycobacterium tuberculosis ClpPs. Our data suggest the presence of a ClpCRP complex in the apicoplast of P. falciparum.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides

This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted in distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Dual nutraceutical nanohybrids of folic acid and calcium containing layered double hydroxides

Dual nutraceutical nanohybrids consisting of organic nutrient, folic acid (FA), and mineral nutrient, calcium, were prepared based on layered double hydroxide (LDH) structure. Among various hybridization methods such as coprecipitation, ion exchange, solid phase reaction and exfoliation-reassembly, it was found that exfoliation-reassembly was the most effective in terms of intercalation of FA moiety between Ca-containing LDH layers. X-ray diffraction patterns and infrared spectra indicated that FA molecules were well stabilized in the interlayer space of LDHs through electrostatic interaction. From the atomic force and scanning electron microscopic studies, particle thickness of LDH was determined to be varied with tens, a few and again tens of nanometers in pristine, exfoliated and reassembled state, respectively, while preserving particle diameter. The result confirmed layer-by-layer hybrid structure of FA and LDHs was obtained by exfoliation-reassembly. Solid UV–vis spectra showed 2-dimensional molecular arrangement of FA moiety in hybrid, exhibiting slight red shift in n→π* and π→π* transition. The chemical formulae of FA intercalated Ca-containing LDH were determined to Ca{sub 1.30}Al(OH){sub 4.6}FA{sub 0.74}·3.33H{sub 2}O and Ca{sub 1.53}Fe(OH){sub 5.06}FA{sub 2.24}·9.94H{sub 2}O by inductively coupled plasma-atomic emission spectroscopy, high performance liquid chromatography and thermogravimetry, showing high nutraceutical content of FA and Ca. - Highlights: • We successfully intercalated FA molecules into Ca-containing LDHs. • Exfoliation-reassembly was proven to be the most effective. • The interaction between LDH and FA were studied by FT-IR and UV–vis spectra. • Thermal stability of FA were enhanced by electrostatic interaction with LDH layers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe{sub 2}O{sub 4} complex oxide catalyst

The CaFe{sub 2}O{sub 4} spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 {sup o}C which was lower than that of ferrite prepared by other methods. CaFe{sub 2}O{sub 4} catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H{sub 2}O{sub 2} (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 {+-} 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 {+-} 2 mol% and minor product phenyl acetaldehyde up to 9 {+-} 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H{sub 2}O{sub 2} molar ratio and solvents on the conversion and product distribution were studied.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Synthesis and characterization of mesoporous-TiO{sub 2} with enhanced photocatalytic activity for the degradation of chloro-phenol

Mesoporous-titania (TiO{sub 2}) photocatalysts have been synthesized using polyethylene glycol (PEG) as a template in dilute acetic acid aqueous solution by hydrothermal process. The effect of PEG molecular weights and thermal treatment on the resultant structure and photocatalytic activity are investigated. Structural and phase compositional properties of the resultant photocatalysts are characterized by transmission electron microscopy, X-ray diffraction and nitrogen sorption analysis. When the molecular weights of PEG vary from 600 to 20,000, the particle sizes of mesoporous structure decrease from 15.1 to 13.3 nm and mean pore sizes increase from 6.9 to 10.6 nm. The chemical reactions of the formation of mesoporous-TiO{sub 2} during its synthesis have been proposed and discussed. The activities of mesoporous-TiO{sub 2} photocatalysts are evaluated and compared with Degussa P-25 using chloro-phenol as a testing compound. The reaction mechanism of photodegradation is also described on the basis of high performance liquid chromatography.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Synthesis of nickel–zinc ferrite magnetic nanoparticle and dye degradation using photocatalytic ozonation

Graphical abstract: Display Omitted Highlights: ► Nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and characterized. ► Dye degradation by photocatalytic ozonation using NZFMN was studied. ► Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. ► Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. ► NZFMN was an effective magnetic nanocatalyst to degrade dyes. -- Abstract: In this paper, nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and its dye degradation ability using photocatalytic ozonation was investigated. The NZFMN was characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM), Fourier transforms infrared (FTIR) and alternative gradient force magnetometer (AGFM). Reactive Red 198 (RR198) and Direct Green 6 (DG6) were used as dye models. UV–vis and ion chromatography (IC) analyses were employed to study dye degradation. The effects of operational parameters on decolorization such as NZFMN dosage, dye concentration, salt and pH were studied. RR198 and DG6 were completely decolorized (100%) by photocatalytic ozonation using NZFMN. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediates. Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. Results showed that the photocatalytic ozonation using NZFMN was a very effective method for dye degradation.

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