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Sample records for 4-vinylcyclohexene diepoxide vcd

  1. Hormonal changes and increased anxiety-like behavior in a perimenopause-animal model induced by 4-vinylcyclohexene diepoxide (VCD) in female rats.

    PubMed

    Reis, F M C V; Pestana-Oliveira, N; Leite, C M; Lima, F B; Brandão, M L; Graeff, F G; Del-Ben, C M; Anselmo-Franci, J A

    2014-11-01

    Perimenopause, a transition period that precedes menopause, is characterized by neuroendocrine, metabolic and behavioral changes, and is associated with increased vulnerability to affective disorders. The decrease in ovarian follicles during perimenopause contributes to a dynamic and complex hormonal milieu that is not yet well characterized. In rodents, 4-vinylcyclohexene diepoxide (VCD) induces a gradual depletion of ovarian follicles, modeling the transition to menopause in women. This study was aimed to investigate, in VCD-treated rats, the hormonal status and the behavior in the elevated plus-maze (EPM), a widely used test to assess anxiety-like behavior. From the postnatal day 28, rats were treated with VCD or vehicle for 15 days. At 80±5 days after the beginning of treatment the experiments were performed at proestrus and diestrus. In the first experiment rats were decapitated, ovary was collected and blood samples were taken for estradiol, progesterone, follicle stimulant hormone (FSH), testosterone, dihydrotestosterone (DHT) and corticosterone measurements. In the second experiment, rats were subjected to the EPM for 5 min, and behavioral categories recorded. Administration of VCD induced follicular depletion as well as an increase of the number of atretic follicles demonstrating the treatment efficacy. The transitional follicular depletion was accompanied by lower progesterone, testosterone and DHT with no changes in the FSH, estradiol and corticosterone plasma levels. On the EPM, rats showed decreased open arm exploration and increased risk assessment behavior, indicating increased anxiety. These findings show that administration of VCD to induce ovarian failure results in endocrine and anxiety-related changes that are similar to the symptoms exhibited by women during menopause transition. Thus, this model seems to be promising in the study of perimenopause-related changes.

  2. Ovotoxicants 4-vinylcyclohexene 1,2-monoepoxide and 4-vinylcyclohexene diepoxide disrupt redox status and modify different electrophile sensitive target enzymes and genes in Drosophila melanogaster.

    PubMed

    Abolaji, Amos O; Kamdem, Jean P; Lugokenski, Thiago H; Farombi, Ebenezer O; Souza, Diogo O; da Silva Loreto, Élgion L; Rocha, João B T

    2015-08-01

    The compounds 4-vinylcyclohexene 1,2-monoepoxide (VCM) and 4-Vinylcyclohexene diepoxide (VCD) are the two downstream metabolites of 4-vinylcyclohexene (VCH), an ovotoxic agent in mammals. In addition, VCM and VCD may be found as by-products of VCH oxidation in the environment. Recently, we reported the involvement of oxidative stress in the toxicity of VCH in Drosophila melanogaster. However, it was not possible to determine the individual contributions of VCM and VCD in VCH toxicity. Hence, we investigated the toxicity of VCM and VCD (10-1000 µM) in flies after 5 days of exposure via the diet. Our results indicated impairments in climbing behaviour and disruptions in antioxidant balance and redox status evidenced by an increase in DCFH oxidation, decreases in total thiol content and glutathione-S-transferase (GST) activity in the flies exposed to VCM and VCD (p<0.05). These effects were accompanied by disruptions in the transcription of the genes encoding the proteins superoxide dismutase (SOD1), kelch-like erythroid-derived cap-n-collar (CNC) homology (ECH)-associated protein 1 (Keap-1), mitogen activated protein kinase 2 (MAPK-2), catalase, Cyp18a1, JAFRAC 1 (thioredoxin peroxidase 1) and thioredoxin reductase 1 (TrxR-1) (p<0.05). VCM and VCD inhibited acetylcholinesterase (AChE) and delta aminolevulinic acid dehydratase (δ-ALA D) activities in the flies (p<0.05). Indeed, here, we demonstrated that different target enzymes and genes were modified by the electrophiles VCM and VCD in the flies. Thus, D. melanogaster has provided further lessons on the toxicity of VCM and VCD which suggest that the reported toxicity of VCH may be mediated by its transformation to VCM and VCD.

  3. Ovotoxicants 4-vinylcyclohexene 1,2-monoepoxide and 4-vinylcyclohexene diepoxide disrupt redox status and modify different electrophile sensitive target enzymes and genes in Drosophila melanogaster

    PubMed Central

    Abolaji, Amos O.; Kamdem, Jean P.; Lugokenski, Thiago H.; Farombi, Ebenezer O.; Souza, Diogo O.; da Silva Loreto, Élgion L.; Rocha, João B.T.

    2015-01-01

    The compounds 4-vinylcyclohexene 1,2-monoepoxide (VCM) and 4-Vinylcyclohexene diepoxide (VCD) are the two downstream metabolites of 4-vinylcyclohexene (VCH), an ovotoxic agent in mammals. In addition, VCM and VCD may be found as by-products of VCH oxidation in the environment. Recently, we reported the involvement of oxidative stress in the toxicity of VCH in Drosophila melanogaster. However, it was not possible to determine the individual contributions of VCM and VCD in VCH toxicity. Hence, we investigated the toxicity of VCM and VCD (10–1000 µM) in flies after 5 days of exposure via the diet. Our results indicated impairments in climbing behaviour and disruptions in antioxidant balance and redox status evidenced by an increase in DCFH oxidation, decreases in total thiol content and glutathione-S-transferase (GST) activity in the flies exposed to VCM and VCD (p<0.05). These effects were accompanied by disruptions in the transcription of the genes encoding the proteins superoxide dismutase (SOD1), kelch-like erythroid-derived cap-n-collar (CNC) homology (ECH)-associated protein 1 (Keap-1), mitogen activated protein kinase 2 (MAPK-2), catalase, Cyp18a1, JAFRAC 1 (thioredoxin peroxidase 1) and thioredoxin reductase 1 (TrxR-1) (p<0.05). VCM and VCD inhibited acetylcholinesterase (AChE) and delta aminolevulinic acid dehydratase (δ-ALA D) activities in the flies (p<0.05). Indeed, here, we demonstrated that different target enzymes and genes were modified by the electrophiles VCM and VCD in the flies. Thus, D. melanogaster has provided further lessons on the toxicity of VCM and VCD which suggest that the reported toxicity of VCH may be mediated by its transformation to VCM and VCD. PMID:26117601

  4. 4-Vinylcyclohexene diepoxide reduces fertility in female Siberian hamsters when treated during their reproductively active and quiescent states.

    PubMed

    Roosa, Kristen A; Mukai, Motoko; Place, Ned J

    2015-01-01

    The industrial compound 4-vinylcyclohexene diepoxide (VCD) destroys ovarian follicles and reduces fertility in rodents, but to date VCD has not been tested in species that experience seasonal anestrus. To determine if VCD destroys follicles when administered during reproductive quiescence, Siberian hamsters were treated with VCD (240mg/kg i.p. daily for 10 days) during short days, and outcomes were compared with reproductively active females that were maintained and treated in long days. Primordial follicle numbers were significantly reduced by VCD under both day lengths, and reproductive quiescence in short days did not appear to render the ovaries less susceptible to VCD-induced follicle depletion. Independent of day length and reproductive state, VCD-treated hamsters weaned substantially fewer offspring than controls. These results suggest that time of year may not be an important consideration for optimizing use of VCD in the field when the target pest species is a seasonally breeding rodent.

  5. Hepatic and renal toxicological evaluations of an industrial ovotoxic chemical, 4-vinylcyclohexene diepoxide, in both sexes of Wistar rats.

    PubMed

    Abolaji, Amos Olalekan; Toloyai, Pere-Ebi; Odeleye, Titilope Deborah; Akinduro, Susan; Teixeira Rocha, Joao Batista; Farombi, Ebenezer Olatunde

    2016-07-01

    4-Vinylcyclohexene diepoxide (VCD) is an industrial occupational health hazard chemical because it induces ovotoxicity in rodents. The current study investigated the impacts of VCD on selected hepatic and renal markers of oxidative stress and inflammation in both sexes of Wistar rats. Thus, male and female rats were randomly distributed into four groups of ten rats per group, and dosed orally with VCD for 28days. The control male and female groups of rats received corn oil only, while each of the three remaining groups of both sexes of rats received VCD (100, 250 and 500mg/kg BW) respectively. Thereafter, biomarkers of hepatic and renal oxidative damage, inflammation and immunohistochemical expressions of iNOS, COX-2, caspase-9 and caspase-3 were evaluated. The results revealed that VCD increased markers of liver and kidney functions, oxidative damage and inflammation, and disrupted the antioxidant homeostasis of the rats (p<0.05). Lastly, VCD enhanced the immunohistochemical expressions of iNOS, COX-2, caspase-9 and caspase-3 in the liver of the rats. Thus, our data imply that VCD induced toxicity in the liver and kidney of rats via the combined impacts of oxidative damage and inflammation. PMID:27258136

  6. Ovarian expressed microsomal epoxide hydrolase: Role in detoxification of 4-vinylcyclohexene diepoxide and regulation by phosphatidylinositol-3 kinase signaling

    SciTech Connect

    Bhattacharya, Poulomi; Sen, Nivedita; Hoyer, Patricia B.; Keating, Aileen F.

    2012-01-01

    4-vinylcyclohexene diepoxide (VCD) is a metabolite of 4-vinylcyclohexene (VCH) which has the potential to be formed in the ovary through CYP2E1 activity. VCD specifically destroys primordial and small primary follicles in the rodent ovary. Mouse ovaries exposed to VCD demonstrate increased mRNA and protein expression of microsomal epoxide hydrolase (mEH), and an inactive tetrol metabolite (4-(1,2-dihydroxy)ethyl-1,2-dihydroxycyclohexane) can be formed in mouse ovarian follicles, potentially through detoxification action of mEH. In contrast, mEH can bioactivate another ovotoxic chemical, 7,12-dimethylbenz[a]anthracene (DMBA) to a more toxic compound, DMBA-3,4-diol-1,2-epoxide. Thus, the present study evaluated a functional role for mEH during detoxification of VCD. Additionally, because inhibition of the phosphatidyinositol-3 kinase (PI3K) signaling pathway in a previous study protected primordial follicles from VCD-induced destruction, but accelerated DMBA-induced ovotoxicity, a role for PI3K in ovarian mEH regulation was evaluated. Using a post-natal day (PND) 4 Fischer 344 rat whole ovary culture system inhibition of mEH using cyclohexene oxide during VCD exposure resulted in a greater (P < 0.05) loss of primordial and small primary follicles relative to VCD-treated ovaries. Also, relative to controls, meh mRNA was increased (P < 0.05) on day 4 of VCD (30 μM) exposure, followed by increased (P < 0.05) mEH protein after 6 days. Furthermore, inhibition of PI3K signaling increased mEH mRNA and protein expression. Thus, these results support a functional role for mEH in the rat ovary, and demonstrate the involvement of PI3K signaling in regulation of ovarian xenobiotic metabolism by mEH. -- Highlights: ► Ovarian mEH functions to metabolize VCD to a less toxic compound. ► mEH expression is increased in a temporal pattern in response to VCD exposure. ► PI3K signaling is involved in regulation of ovarian mEH expression.

  7. Effect of phosphatidylinositol-3 kinase inhibition on ovotoxicity caused by 4-vinylcyclohexene diepoxide and 7, 12-dimethylbenz[a]anthracene in neonatal rat ovaries

    SciTech Connect

    Keating, Aileen F.; Mark, Connie J.; Sen, Nivedita; Sipes, I. Glenn; Hoyer, Patricia B.

    2009-12-01

    4-vinylcyclohexene diepoxide (VCD) is an ovotoxicant that specifically destroys primordial and small primary follicles in the ovaries of mice and rats. In contrast, 7,12-dimethylbenz[a]anthracene (DMBA) is ovotoxic to all ovarian follicle classes. This study investigated phosphatidylinositol-3 kinase signaling involvement in VCD- and DMBA-induced ovotoxicity. Postnatal day (PND) 4 Fischer 344 (F344) rat whole ovaries were cultured for 2-12 days in vehicle control, VCD (30 muM), or DMBA (1 muM), +- PI3 kinase inhibitor LY294002 (20 muM) or its inactive analog LY303511 (20 muM). Following culture, ovaries were histologically evaluated, and healthy follicles were classified and counted. PI3 kinase inhibition had no effect on primordial follicle number, but reduced (P < 0.05) small primary and larger follicles beginning on day 4. VCD caused primordial and small primary follicle loss (P < 0.05) beginning on day 6. With PI3 kinase inhibition, VCD did not affect primordial follicles (P > 0.05) at any time, but did cause loss (P < 0.05) of small primary follicles. DMBA exposure caused primordial and small primary follicle loss (P < 0.05) on day 6. Further, DMBA-induced primordial and small primary follicle loss was greater with PI3 kinase inhibition (P < 0.05) than with DMBA alone. These results support that (1) PI3 kinase mediates primordial to small primary follicle recruitment, (2) VCD, but not DMBA, enhances ovotoxicity by increasing primordial to small primary follicle recruitment, and (3) in addition to xenobiotic-induced ovotoxicity, VCD is also a useful model chemical with which to elucidate signaling mechanisms involved in primordial follicle recruitment.

  8. Involvement of CYP 2E1 enzyme in ovotoxicity caused by 4-vinylcyclohexene and its metabolites

    SciTech Connect

    Rajapaksa, Kathila S.; Cannady, Ellen A.; Sipes, I. Glenn; Hoyer, Patricia B. . E-mail: hoyer@u.arizona.edu

    2007-06-01

    4-Vinylcyclohexene (VCH) is bioactivated by hepatic CYP 2A and 2B to a monoepoxide (VCM) and subsequently to an ovotoxic diepoxide metabolite (VCD). Studies suggest that the ovary can directly bioactivate VCH via CYP 2E1. The current study was designed to evaluate the role of ovarian CYP 2E1 in VCM-induced ovotoxicity. Postnatal day 4 B6C3F{sub 1} and CYP 2E1 wild-type (+/+) and null (-/-) mouse ovaries were cultured (15 days) with VCD (30 {mu}M), 1,2-VCM (125-1000 {mu}M), or vehicle. Twenty-eight days female CYP 2E1 +/+ and -/- mice were dosed daily (15 days; ip) with VCH, 1,2-VCM, VCD or vehicle. Following culture or in vivo dosing, ovaries were histologically evaluated. In culture, VCD decreased (p < 0.05) primordial and primary follicles in ovaries from all three groups of mice. 1,2-VCM decreased (p < 0.05) primordial follicles in B6C3F{sub 1} and CYP 2E1 +/+ ovaries, but not in CYP 2E1 -/- ovaries in culture. 1,2-VCM did not affect primary follicles in any group of mouse ovaries. Conversely, following in vivo dosing, primordial and primary follicles were reduced (p < 0.05) by VCD and VCM in CYP2E1 +/+ and -/-, and by VCH in +/+ mice. The data demonstrate that, whereas in vitro ovarian bioactivation of VCM requires CYP 2E1 enzyme, in vivo CYP 2E1 plays a minimal role. Thus, the findings support that hepatic metabolism dominates the contribution made by the ovary in bioactivation of VCM to its ovotoxic metabolite, VCD. This study also demonstrates the use of a novel ovarian culture system to evaluate ovary-specific metabolism of xenobiotics.

  9. Expression of ovarian microsomal epoxide hydrolase and glutathione S-transferase during onset of VCD-induced ovotoxicity in B6C3F{sub 1} mice

    SciTech Connect

    Keating, Aileen F.; Sipes, I. Glenn; Hoyer, Patricia B.

    2008-07-01

    4-vinylcyclohexene diepoxide (VCD) specifically destroys small pre-antral follicles in the rodent ovary. VCD can be detoxified to an inactive tetrol by microsomal epoxide hydrolase (mEH), or by conjugation to glutathione (GSH) by glutathione S-transferase (GST). Formation of VCD-GSH adducts in the mouse ovary 4 h after VCD exposure (0.57 mmol/kg/day) has been demonstrated. Because the mouse ovary expresses both mEH and GST, expression of mEH and GST pi and mu during a time-course of VCD-induced ovotoxicity was evaluated in a neonatal mouse ovarian culture system. Ovaries from postnatal day 4 (PND4) B6C3F{sub 1} mice were incubated with VCD (15 {mu}M) for 2, 4, 6, 8, 10, 12, or 15 days. Following incubation, ovaries were histologically evaluated, or assessed for mRNA or protein expression. VCD did not cause follicle loss (p > 0.05) on days 2, 4, or 6 of culture. At days 8, 10, 12, and 15, VCD reduced (p < 0.05) both primordial and primary follicle numbers. Increased (p < 0.05) expression of mEH, GST pi and GST mu mRNA was detected after 4 days of VCD exposure. This expression was reduced on days 6 and 8, when follicle loss was underway, but increased (p < 0.05) after 10 days of exposure. mEH and GST pi proteins were elevated (p < 0.05) following 8 days of VCD-exposure however there was no increase in GST mu protein. These findings suggest that with continuous exposure to VCD, increased expression of detoxification enzymes may participate in retarding the onset of follicle loss, but that this loss cannot ultimately be prevented.

  10. Distribution and responsiveness of rat anti-Muellerian hormone during ovarian development and VCD-induced ovotoxicity

    SciTech Connect

    Mark-Kappeler, Connie J.; Sen, Nivedita; Keating, Aileen F.; Sipes, I. Glenn; Hoyer, Patricia B.

    2010-11-15

    Anti-Muellerian hormone (AMH) is produced by granulosa cells in primary to small antral follicles of the adult ovary and helps maintain primordial follicles in a dormant state. The industrial chemical, 4-vinylcyclohexene diepoxide (VCD) causes specific ovotoxicity in primordial and small primary follicles of mice and rats. Previous studies suggest that this ovotoxicity involves acceleration of primordial to primary follicle recruitment via interactions with the Kit/Kit ligand signaling pathway. Because of its accepted role in inhibiting primordial follicle recruitment, the present study was designed to investigate a possible interaction between AMH and VCD-induced ovotoxicity. Protein distribution of AMH was compared in neonatal and adult F344 rat ovaries. AMH protein was visualized by immunofluorescence microscopy in large primary and secondary follicles of the adult ovary, but in small primary follicles in neonatal rat ovaries. In cultured postnatal day (PND) 4 F344 rat ovaries, VCD exposure (30 {mu}M, 2-8 days) decreased (P < 0.05) AMH mRNA (d4-8) and protein (d6-8). Recombinant AMH (100-400 mg/ml) in PND4 ovaries cultured 8 days {+-} VCD (30 {mu}M) caused an increase (P < 0.05) in primordial, and a decrease (P < 0.05) in small primary follicles, supporting that AMH retarded primordial follicle recruitment. However, no concentration of AMH had an effect on VCD-induced ovotoxicity. Whereas, VCD caused a reduction in expression of AMH (d4-d8), it followed previously reported initial disruptions in Kit signaling induced by VCD (d2). Thus, collectively, these results do not support a mechanism whereby VCD causes ovotoxicity via generalized activation of primordial follicle recruitment, but instead provide further support for the specificity of other intracellular mechanisms involved in VCD-induced ovotoxicity.

  11. Glutathione S-transferase class mu regulation of apoptosis signal-regulating kinase 1 protein during VCD-induced ovotoxicity in neonatal rat ovaries

    SciTech Connect

    Bhattacharya, Poulomi; Madden, Jill A.; Sen, Nivedita; Hoyer, Patricia B.; Keating, Aileen F.

    2013-02-15

    4-Vinylcyclohexene diepoxide (VCD) destroys ovarian primordial and small primary follicles via apoptosis. In mice, VCD exposure induces ovarian mRNA expression of glutathione S-transferase (GST) family members, including isoform mu (Gstm). Extra-ovarian GSTM negatively regulates pro-apoptotic apoptosis signal-regulating kinase 1 (ASK1) through protein complex formation, which dissociates during stress, thereby initiating ASK1-induced apoptosis. The present study investigated the ovarian response of Gstm mRNA and protein to VCD. Induction of Ask1 mRNA at VCD-induced follicle loss onset was determined. Ovarian GSTM:ASK1 protein complex formation was investigated and VCD exposure effects thereon evaluated. Phosphatidylinositol-3 kinase (PI3K) regulation of GSTM protein was also studied. Postnatal day (PND) 4 rat ovaries were cultured in control media ± 1) VCD (30 μM) for 2–8 days; 2) VCD (30 μM) for 2 days, followed by incubation in control media for 4 days (acute VCD exposure); or 3) LY294002 (20 μM) for 6 days. VCD exposure did not alter Gstm mRNA expression, however, GSTM protein increased (P < 0.05) after 6 days of both the acute and chronic treatments. Ask1 mRNA increased (0.33-fold; P < 0.05) relative to control after 6 days of VCD exposure. Ovarian GSTM:ASK1 protein complex formation was confirmed and, relative to control, the amount of GSTM bound to ASK1 increased 33% (P < 0.05) by chronic but with no effect of acute VCD exposure. PI3K inhibition increased (P < 0.05) GSTM protein by 40% and 71% on d4 and d6, respectively. These findings support involvement of GSTM in the ovarian response to VCD exposure, through regulation of pro-apoptotic ASK1. - Highlights: ► GSTM protein increases in response to ovarian VCD exposure. ► VCD increases Ask1 mRNA at the onset of follicle loss. ► Ovarian GSTM binds more ASK1 protein during VCD-induced ovotoxicity. ► PI3K regulates ovarian GSTM protein.

  12. ANG II-induced hypertension in the VCD mouse model of menopause is prevented by estrogen replacement during perimenopause.

    PubMed

    Pollow, Dennis P; Romero-Aleshire, Melissa J; Sanchez, Jessica N; Konhilas, John P; Brooks, Heddwen L

    2015-12-15

    Premenopausal females are resistant to the development of hypertension, and this protection is lost after the onset of menopause, resulting in a sharp increase in disease onset and severity. However, it is unknown how a fluctuating ovarian hormone environment during the transition from perimenopause to menopause impacts the onset of hypertension, and whether interventions during perimenopause prevent disease onset after menopause. A gradual transition to menopause was induced by repeated daily injections of 4-vinylcyclohexene diepoxide (VCD). ANG II (800 ng·kg(-1)·min(-1)) was infused into perimenopausal and menopausal female mice for 14 days. A separate cohort of mice received 17β-estradiol replacement during perimenopause. ANG II infusion produced significantly higher mean arterial pressure (MAP) in menopausal vs. cycling females, and 17β-estradiol replacement prevented this increase. In contrast, MAP was not significantly different when ANG II was infused into perimenopausal and cycling females, suggesting that female resistance to ANG II-induced hypertension is intact during perimenopause. ANG II infusion caused a significant glomerular hypertrophy, and hypertrophy was not impacted by hormonal status. Expression levels of aquaporin-2 (AQP2), a collecting duct protein, have been suggested to reflect blood pressure. AQP2 protein expression was significantly downregulated in the renal cortex of the ANG II-infused menopause group, where blood pressure was increased. AQP2 expression levels were restored to control levels with 17β-estradiol replacement. This study indicates that the changing hormonal environment in the VCD model of menopause impacts the severity of ANG II-induced hypertension. These data highlight the utility of the ovary-intact VCD model of menopause as a clinically relevant model to investigate the physiological mechanisms of hypertension that occur in women during the transition into menopause.

  13. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

    PubMed

    Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M

    2015-06-15

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

  14. Involvement of oxidative stress in 4-vinylcyclohexene-induced toxicity in Drosophila melanogaster.

    PubMed

    Abolaji, Amos Olalekan; Kamdem, Jean Paul; Lugokenski, Thiago Henrique; Nascimento, Thallita Kalar; Waczuk, Emily Pansera; Farombi, Ebenezer Olatunde; Loreto, Élgion Lúcio da Silva; Rocha, João Batista Teixeira

    2014-06-01

    4-Vinylcyclohexene (VCH) is a dimer of 1,3-butadiene produced as a by-product of pesticides, plastic, rubber, flame retardants, and tire production. Although, several studies have reported the ovotoxicity of VCH, information on a possible involvement of oxidative stress in the toxicity of this occupational chemical is scarce. Hence, this study was carried out to investigate further possible mechanisms of toxicity of VCH with a specific emphasis on oxidative stress using a Drosophila melanogaster model. D. melanogaster (both genders) of 1 to 3 days old were exposed to different concentrations of VCH (10 µM-1 mM) in the diet for 5 days. Subsequently, the survival and negative geotaxis assays and the quantification of reactive oxygen species (ROS) generation were determined. In addition, we evaluated RT-PCR expressions of selected oxidative stress and antioxidant mRNA genes (HSP27, 70, and 83, SOD, Nrf-2, MAPK2, and catalase). Furthermore, catalase, glutathione-S-transferase (GST), delta aminolevulinic acid dehydratase (δ-ALA-D), and acetylcholinesterase (AChE) activities were determined. VCH exposure impaired negative geotaxic behavior and induced the mRNA of SOD, Nrf-2, and MAPK2 genes expressions. There were increases in catalase and ROS production, as well as inhibitions of GST, δ-ALA-D, and AChE activities (P<0.05). Our results suggest that the VCH mechanism of toxicity is associated with oxidative damage, as evidenced by the alteration in the oxidative stress-antioxidant balance, and possible neurotoxic consequences due to decreased AChE activity, and impairments in negative geotaxic behavior. Thus, we conclude that D. melanogaster is a useful model for investigating the toxicity of VCH exposure, and here, we have provided further insights on the mechanism of VCH-induced toxicity.

  15. Effect of bcl-2 overexpression in mice on ovotoxicity caused by 4-vinylcyclohexene

    SciTech Connect

    Flaws, Jodi A.; Marion, Samuel L.; Miller, Kimberly P.; Christian, Patricia J.; Babus, Janice K.; Hoyer, Patricia B. . E-mail: hoyer@u.arizona.edu

    2006-08-15

    The occupational chemical 4-vinylcyclohexene (VCH) destroys small preantral ovarian follicles in mice following repeated daily dosing. The cell survival gene bcl-2 is thought to protect against follicular death during embryogenesis because primordial follicle numbers in newborn bcl-2 overexpressing (OE) mice are greater than in wild-type (WT) controls. Thus, this study was designed to determine if overexpression of bcl-2 protects against VCH-induced follicle loss during embryonic development. Pregnant bcl-2 OE or WT mice were dosed (p.o.) daily with VCH (500 mg/kg) or sesame oil (vehicle control) on days 8-18 of pregnancy. Ovaries were collected from moms and female pups on pup postnatal day (PND) 8. Nonpregnant OE and WT females were also treated with VCH (500 mg/kg p.o.) or vehicle and evaluated in the same manner. As previously reported, ovaries from PND8 OE female pups contained 50% more primordial follicles than WT pups (P < 0.05). Unlike WT pups, relative to vehicle controls, in utero exposure to VCH resulted in a reduction in primordial (25% of control), primary (38% of control), and secondary (33% of control) follicles in ovaries of OE pups (P < 0.05). VCH had no significant effect on follicle numbers in OE or WT moms. Conversely, in nonpregnant adults, VCH did not affect WT mice but caused loss of primordial (55% of control), primary (51% of control), and secondary (69% of control) follicles in OE mice (P < 0.05). These results demonstrate that bcl-2 overexpression does not protect against, but instead increases susceptibility to VCH-induced follicle loss in transplacentally exposed or in nonpregnant mice.

  16. Differential profile of letrozole and exemestane on bone turnover markers in vinylcyclohexene diepoxide treated ovotoxic female mice.

    PubMed

    Kalam, Abul; Talegaonkar, Sushama; Vohora, Divya

    2016-10-01

    The third generation aromatase inhibitors are currently the drugs of choice for the treatment of early and advanced breast cancer in postmenopausal women. One of the significant limiting factor during therapy is their negative impact on bone health. In this study, we compared the effects of a nonsteroidal (letrozole) and a steroidal aromatase inhibitor (exemestane) on bone mineral density and markers of bone turnover including alkaline phosphatase (ALP), tartrate-resistant acid phosphatase (TRAP), hydroxyproline (HxP), receptor activator of nuclear factor kappa B ligand (RANKL), sclerostin, and dickkopf-1 (DKK-1) in vinylcyclohexene diepoxide (VCD)-induced ovotoxic female mice. VCD administration for 15 days mimicked a postmenopausal state with reduced serum estradiol levels. Ovotoxicity was accompanied by reduced ALP, HxP and enhanced TRAP, sclerostin and DKK-1 activity in femoral epiphysis and lumbar vertebrae of mice. While letrozole (1 mg/kg) administration for 1 month enhanced bone turnover in ovotoxic mice, exemestane (3.25 mg/kg) was devoid of such effects in both normal and ovotoxic mice. The latter, however, reduced ALP in femoral epiphysis of ovotoxic mice. Letrozole depleted estradiol levels in ovotoxic mice and enhanced RANKL activity while exemestane neither affected estradiol nor RANKL in both normal and ovotoxic mice, and enhanced sclerostin and DKK-1 in femoral epiphysis only. The study indicates that the two aromatase inhibitors possesses differential profile in terms of their effects on bone and that exemestane could be a better option for the treatment of breast cancer in postmenopausal women at least in terms of its effects on bone. PMID:27279630

  17. Differential profile of letrozole and exemestane on bone turnover markers in vinylcyclohexene diepoxide treated ovotoxic female mice.

    PubMed

    Kalam, Abul; Talegaonkar, Sushama; Vohora, Divya

    2016-10-01

    The third generation aromatase inhibitors are currently the drugs of choice for the treatment of early and advanced breast cancer in postmenopausal women. One of the significant limiting factor during therapy is their negative impact on bone health. In this study, we compared the effects of a nonsteroidal (letrozole) and a steroidal aromatase inhibitor (exemestane) on bone mineral density and markers of bone turnover including alkaline phosphatase (ALP), tartrate-resistant acid phosphatase (TRAP), hydroxyproline (HxP), receptor activator of nuclear factor kappa B ligand (RANKL), sclerostin, and dickkopf-1 (DKK-1) in vinylcyclohexene diepoxide (VCD)-induced ovotoxic female mice. VCD administration for 15 days mimicked a postmenopausal state with reduced serum estradiol levels. Ovotoxicity was accompanied by reduced ALP, HxP and enhanced TRAP, sclerostin and DKK-1 activity in femoral epiphysis and lumbar vertebrae of mice. While letrozole (1 mg/kg) administration for 1 month enhanced bone turnover in ovotoxic mice, exemestane (3.25 mg/kg) was devoid of such effects in both normal and ovotoxic mice. The latter, however, reduced ALP in femoral epiphysis of ovotoxic mice. Letrozole depleted estradiol levels in ovotoxic mice and enhanced RANKL activity while exemestane neither affected estradiol nor RANKL in both normal and ovotoxic mice, and enhanced sclerostin and DKK-1 in femoral epiphysis only. The study indicates that the two aromatase inhibitors possesses differential profile in terms of their effects on bone and that exemestane could be a better option for the treatment of breast cancer in postmenopausal women at least in terms of its effects on bone.

  18. Asthma: vocal cord dysfunction (VCD) and other dysfunctional breathing disorders.

    PubMed

    Balkissoon, Ron; Kenn, Klaus

    2012-12-01

    Vocal cord dysfunction (VCD) and dysfunctional breathing (DB) disorders may mimic or coexist with asthma, leading to overtreatment with corticosteroids with consequent morbidity. Iatrogenic complications can be averted by early and correct diagnosis. VCD, also termed paradoxical vocal fold motion disorder (PVFMD), is characterized by intermittent paradoxical adduction of the vocal cords, mainly during inspiration, leading to airflow obstruction and dyspnea. Patients with VCD may have repetitive emergency room visits due to acute dyspnea (mimicking exacerbations of asthma). In the seminal descriptions of VCD, young women (often with psychiatric issues) predominated; however, other groups at increased risk for developing VCD include elite athletes, military recruits, and individuals exposed to irritants (inhaled or aspirated). Chronic postnasal drip, laryngopharyngeal reflux (LPR), and gastroesophageal reflux (GER) may lead to laryngeal hyperresponsiveness. The diagnosis of VCD may be difficult because physical exam and spirometry may be normal between episodes. During symptomatic episodes, spirometry typically reveals variable extrathoracic airway obstruction (truncated inspiratory flow volume loop). The gold standard for identifying VCD is flexible fiberoptic rhinolaryngoscopy. Management of VCD includes identification and treatment of underlying disorders (eg, chronic postnasal drip, LPR, GER, anxiety, depression) and a multidisciplinary approach (including highly trained speech therapists). Speech therapy and biofeedback play a critical role in teaching techniques to override various dysfunctional breathing habits. When postnasal drip, LPR, or GER coexist, these disorders should be aggressively treated. With successful therapy, corticosteroids can often be discontinued. During severe, acute episodes of VCD, therapeutic strategies include heliox (80% helium/20% oxygen), topical lidocaine, anxiolytics, and superior laryngeal blocks with Clostridium botulinum toxin

  19. VCD Studies on Chiral Characters of Metal Complex Oligomers

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes. PMID:23296273

  20. Application of improved technology to a preprototype vapor compression distillation /VCD/ water recovery subsystem

    NASA Technical Reports Server (NTRS)

    Johnson, K. L.; Reysa, R. P.; Fricks, D. H.

    1981-01-01

    Vapor compression distillation (VCD) is considered the most efficient water recovery process for spacecraft application. This paper reports on a preprototype VCD which has undergone the most extensive operational and component development testing of any VCD subsystem to date. The component development effort was primarily aimed at eliminating corrosion and the need for lubrication, upgrading electronics, and substituting nonmetallics in key rotating components. The VCD evolution is documented by test results on specific design and/or materials changes. Innovations worthy of further investigation and additional testing are summarized for future VCD subsystem development reference. Conclusions on experience gained are presented.

  1. Revisiting an old concept: the coupled oscillator model for VCD. Part 2: implications of the generalised coupled oscillator mechanism for the VCD robustness concept.

    PubMed

    Nicu, Valentin Paul

    2016-08-01

    Using two illustrative examples it is shown that the generalised coupled oscillator (GCO) mechanism implies that the stability of the VCD sign computed for a given normal mode is not reflected by the magnitude of the ratio ζ between the rotational strength and dipole strength of the respective mode, i.e., the VCD robustness criterium proposed by Góbi and Magyarfalvi. The performed VCD GCO analysis brings further insight into the GCO mechanism and also into the VCD robustness concept. First, it shows that the GCO mechanism can be interpreted as a VCD resonance enhancement mechanism, i.e. very large VCD signals can be observed when the interacting molecular fragments are in favourable orientation. Second, it shows that the uncertainties observed in the computed VCD signs are associated to uncertainties in the relative orientation of the coupled oscillator fragments and/or to uncertainties in the predicted nuclear displacement vectors, i.e. not uncertainties in the computed magnetic dipole transition moments as was originally assumed. Since it is able to identify such situations easily, the VCD GCO analysis can be used as a VCD robustness analysis.

  2. A method to study the impact of chemically-induced ovarian failure on exercise capacity and cardiac adaptation in mice.

    PubMed

    Chen, Hao; Perez, Jessica N; Constantopoulos, Eleni; McKee, Laurel; Regan, Jessica; Hoyer, Patricia B; Brooks, Heddwen L; Konhilas, John

    2014-04-07

    The risk of cardiovascular disease (CVD) increases in post-menopausal women, yet, the role of exercise, as a preventative measure for CVD risk in post-menopausal women has not been adequately studied. Accordingly, we investigated the impact of voluntary cage-wheel exercise and forced treadmill exercise on cardiac adaptation in menopausal mice. The most commonly used inducible model for mimicking menopause in women is the ovariectomized (OVX) rodent. However, the OVX model has a few dissimilarities from menopause in humans. In this study, we administered 4-vinylcyclohexene diepoxide (VCD) to female mice, which accelerates ovarian failure as an alternative menopause model to study the impact of exercise in menopausal mice. VCD selectively accelerates the loss of primary and primordial follicles resulting in an endocrine state that closely mimics the natural progression from pre- to peri- to post-menopause in humans. To determine the impact of exercise on exercise capacity and cardiac adaptation in VCD-treated female mice, two methods were used. First, we exposed a group of VCD-treated and untreated mice to a voluntary cage wheel. Second, we used forced treadmill exercise to determine exercise capacity in a separate group VCD-treated and untreated mice measured as a tolerance to exercise intensity and endurance.

  3. Results of the Vapor Compression Distillation Flight Experiment (VCD-FE)

    NASA Technical Reports Server (NTRS)

    Hutchens, Cindy; Graves, Rex

    2004-01-01

    Vapor Compression Distillation (VCD) is the chosen technology for urine processing aboard the International Space Station (ISS). Key aspects of the VCD design have been verified and significant improvements made throughout the ground;based development history. However, an important element lacking from previous subsystem development efforts was flight-testing. Consequently, the demonstration and validation of the VCD technology and the investigation of subsystem performance in micro-gravity were the primary goals of the VCD-FE. The Vapor Compression Distillation Flight Experiment (VCD-E) was a flight experiment aboard the Space Shuttle Columbia during the STS-107 mission. The VCD-FE was a full-scale developmental version of the Space Station Urine Processor Assembly (UPA) and was designed to test some of the potential micro-gravity issues with the design. This paper summarizes the experiment results.

  4. Mate preference for dominant vs. subordinate males in young female Syrian hamsters (Mesocricetus auratus) following chemically-accelerated ovarian follicle depletion.

    PubMed

    Roosa, Kristen A; Place, Ned J

    2015-12-01

    Life history theory predicts that selectivity for mates generally declines as females age. We previously demonstrated this phenomenon in Syrian hamsters (Mesocricetus auratus), in that older females showed reduced preference for dominant over subordinate males. To test the hypothesis that decreased reproductive quality due to aging reduces mate preference, we decoupled reproductive and chronological age by treating young female hamsters with 4-vinylcyclohexene diepoxide (VCD), which destroys ovarian follicles and functionally accelerates ovarian follicle depletion without compromising the general health of rodents. In this study, VCD effectively reduced follicle numbers in young Syrian hamsters. VCD-treated and control females were allowed to choose between a dominant and a subordinate male in a Y-maze on the day of proestrus. Both VCD-treated and control females demonstrated preference for the dominant male by leaving a greater proportion of vaginal scent marks near him, which is a behavior that females display when soliciting prospective mates. However, there was no effect of treatment on the proportion of vaginal scent marks left for the dominant male. Furthermore, ovarian follicle numbers were not significantly correlated with any behaviors in either group. We conclude that accelerated ovarian follicle depletion does not reduce mate preference in young female hamsters.

  5. Dual modality imaging of a novel rat model of ovarian carcinogenesis

    NASA Astrophysics Data System (ADS)

    Kanter, Elizabeth; Walker, Ross; Marion, Sam; Brewer, Molly A.; Hoyer, Patricia B.; Barton, Jennifer K.

    2006-07-01

    Ovarian cancer is the fifth leading cause of cancer death in women, in part because of the limited knowledge about early stage disease. We develop a novel rat model of ovarian cancer and perform a pilot study to examine the harvested ovaries with complementary optical imaging modalities. Rats are exposed to repeated daily dosing (20 days) with 4-vinylcyclohexene diepoxide (VCD) to cause early ovarian failure (model for postmenopause), and ovaries are directly exposed to 7,12-dimethylbenz(a)anthracene (DMBA) to cause abnormal ovarian proliferation and neoplasia. Harvested ovaries are examined with optical coherence tomography (OCT) and light-induced fluorescence (LIF) at one, three, and five months post-DMBA treatment. VCD causes complete ovarian follicle depletion within 8 months after onset of dosing. DMBA induces abnormal size, cysts, and neoplastic changes. OCT successfully visualizes normal and abnormal structures (e.g., cysts, bursa, follicular remnant degeneration) and the LIF spectra show statistically significant changes in the ratio of average emission intensity at 390:450 nm between VCD-treated ovaries and both normal cycling and neoplastic DMBA-treated ovaries. Overall, this pilot study demonstrates the feasibility of both the novel animal model for ovarian cancer and the ability of optical imaging techniques to visualize ovarian function and health.

  6. IR-Raman-VCD study of R-(+)-Pulegone: Influence of the solvent

    NASA Astrophysics Data System (ADS)

    Aviles-Moreno, Juan Ramón; Ureña Horno, Elena; Partal Ureña, Francisco; López González, Juan Jesús

    2011-08-01

    R-(+)-Pulegone is a natural monoterpene obtained from the essential oils of a variety of plants. It is used in flavouring agents, perfumery and aromatherapy. In this work, a study of the molecular structure and the infrared and Raman spectra of this chemical is presented. Theoretical calculations reveal the existence of two conformers depending on the position of the methyl group (axial and equatorial), being the equatorial conformer the most stable. A complete and reliable assignment of the IR and Raman spectra of the title compound is made, and the results are used to carry out a detailed interpretation of the VCD spectrum of this compound in the 4000-900 cm -1 region. Finally, the influence of the solvent in the VCD bands (intensity and sign) has been tested comparing the neat liquid spectrum with the VCD spectra recorded with four solvents.

  7. Revisiting an old concept: the coupled oscillator model for VCD. Part 1: the generalised coupled oscillator mechanism and its intrinsic connection to the strength of VCD signals.

    PubMed

    Nicu, Valentin Paul

    2016-08-01

    Motivated by the renewed interest in the coupled oscillator (CO) model for VCD, in this work a generalised coupled oscillator (GCO) expression is derived by introducing the concept of a coupled oscillator origin. Unlike the standard CO expression, the GCO expression is exact within the harmonic approximation. Using two illustrative example molecules, the theoretical concepts introduced here are demonstrated by performing a GCO decomposition of the rotational strengths computed using DFT. This analysis shows that: (1) the contributions to the rotational strengths that are normally neglected in the standard CO model can be comparable to or larger than the CO contribution, and (2) the GCO mechanism introduced here can affect the VCD intensities of all types of modes in symmetric and asymmetric molecules.

  8. Gender differences in the metabolism of 1,3-butadiene to butadiene diepoxide in Sprague-Dawley rats

    SciTech Connect

    Thornton-Manning, J.R.; Dahl, A.R.; Bechtold, W.E.

    1995-12-01

    1,3-Butadiene (BD), a gaseous compound used in the production of rubber, is a potent carcinogen in mice and a weak carcinogen in rats. The mechanism of BD-induced carcinogenicity is thought to involve genotoxic effects of its reactive epoxide metabolites butadiene monoepoxide (BDO) and butadiene diepoxide (BDO{sub 2}). Studies in our laboratory have shown that levels of the epoxides, particularly BDO{sub 2}, are greater in mice-the more sensitive species-than rats. While both epoxides are genotoxic in a number of assays, BDO{sub 2} is mutagenic in TK6 human lymphoblastoid cells at concentrations approximately 100-fold lower than BDO. Species differences in carcinogenicity of BD have posed a dilemma to investigators deciding which animal model is most appropriate for BD risk assessment.

  9. VCD spectroscopy as an excellent probe of chiral metal complexes containing a carbon monoxide vibrational chromophore.

    PubMed

    Fusè, Marco; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Zerla, Daniele; Rimoldi, Isabella; Contini, Alessandro; Cesarotti, Edoardo

    2015-06-01

    Vibrational circular dichroism, VCD, gives evidence that the carbon monoxide chromophore in a heteroleptic cyclopentadienyl Ru(ii)-carbonyl complex is very sensitive to the chirality of the metal centre and becomes an excellent probe to define the configuration of chiral metal complexes.

  10. Induced solvent chirality: A VCD study of camphor in CDCl 3

    NASA Astrophysics Data System (ADS)

    Debie, Elke; Jaspers, Lize; Bultinck, Patrick; Herrebout, Wouter; Veken, Benjamin Van Der

    2008-01-01

    It is shown how the presence of a chiral compound in solution induces chirality in the surrounding solvent molecules. Using Vibrational Circular Dichroism on camphor dissolved in deuterated chloroform, it is found that the C-D stretch in the latter indeed becomes VCD active. The experimental results agree with ab initio computed spectra for 1:1 associations between the solvent and solute.

  11. Phase III trial of bortezomib, cyclophosphamide and dexamethasone (VCD) versus bortezomib, doxorubicin and dexamethasone (PAd) in newly diagnosed myeloma.

    PubMed

    Mai, E K; Bertsch, U; Dürig, J; Kunz, C; Haenel, M; Blau, I W; Munder, M; Jauch, A; Schurich, B; Hielscher, T; Merz, M; Huegle-Doerr, B; Seckinger, A; Hose, D; Hillengass, J; Raab, M S; Neben, K; Lindemann, H-W; Zeis, M; Gerecke, C; Schmidt-Wolf, I G H; Weisel, K; Scheid, C; Salwender, H; Goldschmidt, H

    2015-08-01

    We aimed at demonstrating non-inferiority of bortezomib/cyclophosphamide/dexamethasone (VCD) compared to bortezomib/doxorubicin/dexamethasone (PAd) induction therapy with respect to very good partial response rates or better (⩾VGPR) in 504 newly diagnosed, transplant-eligible multiple myeloma patients. VCD was found to be non-inferior to PAd with respect to ⩾VGPR rates (37.0 versus 34.3%, P=0.001). The rates of progressive disease (PD) were 0.4% (VCD) versus 4.8% (PAd; P=0.003). In the PAd arm, 11 of 12 patients with PD had either renal impairment (creatinine ⩾2 mg/dl) at diagnosis or the cytogenetic abnormality gain 1q21, whereas no PD was observed in these subgroups in the VCD arm. Leukocytopenia/neutropenia (⩾3°) occurred more frequently in the VCD arm (35.2% versus 11.3%, P<0.001). Neuropathy rates (⩾2°) were higher in the PAd group (14.9 versus 8.4%, P=0.03). Serious adverse events, both overall and those related to thromboembolic events, were higher in the PAd group (32.7 versus 24.0%, P=0.04 and 2.8 versus 0.4%, P=0.04). Stem cell collection was not impeded by VCD. VCD is as effective as PAd in terms of achieving ⩾VGPR rates with fewer PD and has a favorable toxicity profile. Therefore, VCD is preferable to PAd as induction therapy. PMID:25787915

  12. Analysis of the major chiral compounds of Artemisia herba-alba essential oils (EOs) using reconstructed vibrational circular dichroism (VCD) spectra: En route to a VCD chiral signature of EOs.

    PubMed

    Said, Mohammed El-Amin; Vanloot, Pierre; Bombarda, Isabelle; Naubron, Jean-Valère; Dahmane, El Montassir; Aamouche, Ahmed; Jean, Marion; Vanthuyne, Nicolas; Dupuy, Nathalie; Roussel, Christian

    2016-01-15

    An unprecedented methodology was developed to simultaneously assign the relative percentages of the major chiral compounds and their prevailing enantiomeric form in crude essential oils (EOs). In a first step the infrared (IR) and vibrational circular dichroism (VCD) spectra of the crude essential oils were recorded and in a second step they were modelized as a linear weighted combination of the IR and VCD spectra of the individual spectra of pure enantiomer of the major chiral compounds present in the EOs. The VCD spectra of enantiomer of known enantiomeric excess shall be recorded if they are not yet available in a library of VCD spectra. For IR, the spectra of pure enantiomer or racemic mixture can be used. The full spectra modelizations were performed using a well known and powerful mathematical model (least square estimation: LSE) which resulted in a weighting of each contributing compound. For VCD modelization, the absolute value of each weighting represented the percentage of the associate compound while the attached sign addressed the correctness of the enantiomeric form used to build the model. As an example, a model built with the non-prevailing enantiomer will show a negative sign of the weighting value. For IR spectra modelization, the absolute value of each weighting represented the percentage of the compounds without of course accounting for the chirality of the prevailing enantiomers. Comparison of the weighting values issuing from IR and VCD spectra modelizations is a valuable source of information: if they are identical, the EOs are composed of nearly pure enantiomers, if they are different the chiral compounds of the EOs are not in an optically pure form. The method was applied on four samples of essential oil of Artemisia herba-alba in which the three major compounds namely (-)-α-thujone, (+)-β-thujone and (-)-camphor were found in different proportions as determined by GC-MS and chiral HPLC using polarimetric detector. In order to validate the

  13. Analysis of the major chiral compounds of Artemisia herba-alba essential oils (EOs) using reconstructed vibrational circular dichroism (VCD) spectra: En route to a VCD chiral signature of EOs.

    PubMed

    Said, Mohammed El-Amin; Vanloot, Pierre; Bombarda, Isabelle; Naubron, Jean-Valère; Dahmane, El Montassir; Aamouche, Ahmed; Jean, Marion; Vanthuyne, Nicolas; Dupuy, Nathalie; Roussel, Christian

    2016-01-15

    An unprecedented methodology was developed to simultaneously assign the relative percentages of the major chiral compounds and their prevailing enantiomeric form in crude essential oils (EOs). In a first step the infrared (IR) and vibrational circular dichroism (VCD) spectra of the crude essential oils were recorded and in a second step they were modelized as a linear weighted combination of the IR and VCD spectra of the individual spectra of pure enantiomer of the major chiral compounds present in the EOs. The VCD spectra of enantiomer of known enantiomeric excess shall be recorded if they are not yet available in a library of VCD spectra. For IR, the spectra of pure enantiomer or racemic mixture can be used. The full spectra modelizations were performed using a well known and powerful mathematical model (least square estimation: LSE) which resulted in a weighting of each contributing compound. For VCD modelization, the absolute value of each weighting represented the percentage of the associate compound while the attached sign addressed the correctness of the enantiomeric form used to build the model. As an example, a model built with the non-prevailing enantiomer will show a negative sign of the weighting value. For IR spectra modelization, the absolute value of each weighting represented the percentage of the compounds without of course accounting for the chirality of the prevailing enantiomers. Comparison of the weighting values issuing from IR and VCD spectra modelizations is a valuable source of information: if they are identical, the EOs are composed of nearly pure enantiomers, if they are different the chiral compounds of the EOs are not in an optically pure form. The method was applied on four samples of essential oil of Artemisia herba-alba in which the three major compounds namely (-)-α-thujone, (+)-β-thujone and (-)-camphor were found in different proportions as determined by GC-MS and chiral HPLC using polarimetric detector. In order to validate the

  14. Life testing of the vapor compression distillation urine processor assembly (VCD/UPA) at the Marshall Space Flight Center.

    PubMed

    Wieland, P

    1998-01-01

    Wastewater and urine generated on the International Space Station (ISS) will be processed to recover pure water using vapor compression distillation (VCD). To verify the long-term reliability and performance of the VCD Urine Processor Assembly (UPA), life testing was performed at the Marshall Space Flight Center (MSFC) from January 1993 to April 1996. Two UPAs, the VCD-5 and VCD-5A, were tested for 204 days and 665 days, respectively. The compressor gears and the distillation centrifuge drive belt were found to have operating lives of approximately 4800 h, equivalent to 3.9 years of operation on ISS for a crew of three at an average processing rate of 1.76 kg/h (3.87 lb/h). Precise alignment of the flex-splines of the fluids and purge pump motor drives is essential to avoid premature failure after about 400 h of operation. Results indicate that, with some design and procedural modifications and suitable quality control, the required performance and operational life can be met with the VCD/UPA. PMID:11540460

  15. Life Testing of the Vapor Compression Distillation Urine Processing Assembly (VCD/UPA) at the Marshall Space Flight Center

    NASA Technical Reports Server (NTRS)

    Wieland, Paul O.

    1998-01-01

    Wastewater and urine generated on the International Space Station will be processed to recover pure water. The method selected is vapor compression distillation (VCD). To verify the long-term reliability and performance of the VCD Urine Processing Assembly (UPA), accelerated life testing was performed at the Marshall Space Flight Center (MSFC) from January 1993 to April 1996. Two UPAS, the VCD-5 and VCD-5A, were tested for 204 days and 665 days, respectively. The compressor gears and the distillation centrifuge drive belt were found to have an operating life of approximately 4800 hours. Precise alignment of the flex-spline of the fluids pump is essential to avoid failure of the pump after about 400 hours of operation. Also, leakage around the seals of the drive shaft of the fluids pump and purge pump must be eliminated for continued good performance. Results indicate that, with some design and procedural modifications and suitable quality control, the required performance and operational life can be met with the VCD/UPA.

  16. A mechanistic assessment of 1,3-butadiene diepoxide-induced inhibition of uterine deciduoma proliferation in pseudopregnant rats.

    PubMed

    Spencer, F; Chi, L; Zhu, M

    2001-01-01

    Butadiene diepoxide (BDE), a reactive metabolite of 1,3-butadiene that is an important industrial chemical used in synthetic rubber production causes a dose-dependent inhibition of deciduoma development in pseudopregnant Sprague-Dawley rats. This study used 4 daily i.p. BDE doses of 0.20, 0.25, 0.30, 0.35, or 0.40 to characterize mechanisms that may be responsible for the antideciduoma effect. Pseudopregnant rats were treated either before (pseudopregnancy [PPG] days 1-4) or after (PPG days 5-9) deciduoma induction by endometrial trauma with a blunt needle. Animals were killed on PPG day 9 and evaluated for serum progesterone and endometrial protein and DNA. RT-PCR was used to measure message for estrogen receptor (ER) alpha and pituitary adenylate cyclase-activating polypeptide (PACAP). Substrate zymography and Western blotting were used respectively to measure matrix metalloproteinase (MMP)-9 and inducible nitric oxide synthase. The antideciduoma effects of BDE were associated with decreases in endometrial weight, protein, and DNA, with decreases in serum progesterone, and with decreases in PACAP message and MMP-9. A reduction in NOS was identified at the highest dose of BDE. Message for estrogen receptor (ER) alpha was not affected at any dose. We conclude that the reduction in decidual proliferation was direct and appeared to be associated with either 1) a decrease in the effectiveness of the deciduogenic stimulation and/or a weakened endometrial sensitivity to the stimulus; or 2) an effect on deciduoma development. Molecular mechanisms that apparently contributed to BDE inhibition of decidual metabolism included the synthesis of protein and DNA involved in decidual growth, the synthesis and activation of a matrix metalloproteinase for degradation of the extracellular matrix that is essential for tissue remodeling during deciduoma development, and the nitric oxide/nitric oxide synthase and pituitary adenylate cyclase-activating peptide systems that are involved

  17. XRD and VCD: a marriage of love or convenience? Honeymoon around a cyclic urea derivative.

    PubMed

    Gherase, Dragos; Naubron, Jean-Valère; Roussel, Christian; Giorgi, Michel

    2012-07-01

    The structures and absolute configurations of the enantiomers (3aR,8aR)-2,2-dimethyl-4,4,8,8-tetraphenyl-4,5,6,7,8,8a-hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.33-hydrate, C(32)H(30)N(2)O(3)·0.33H(2)O, (Ia), and (3aS,8aS)-2,2-dimethyl-4,4,8,8-tetraphenyl-4,5,6,7,8,8a-hexahydro-3aH-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 0.39-hydrate, C(32)H(30)N(2)O(3)·0.39H(2)O, (Ib), have been elucidated unambiguously using the complementary power of single-crystal X-ray diffraction (XRD) and vibrational circular dichroism (VCD). The enantiomers crystallize in the Sohncke space group P2(1)2(1)2 and pack as dimers stabilized by two symmetric hydrogen bonds involving one amide group each of the cyclic urea moiety. This double interaction is capped by a water molecule that partially occupies a site lying on the twofold axis and forms an uncommon hydrogen bond between the two monomers. A comparison between the solid-state VCD characterizations and the Bayesian statistics on Bijvoet differences determined from the XRD measurements reveals a tendency towards the correct determination of the absolute configuration by this latter method.

  18. Solvent-induced conformational changes of O-phenyl-cinchonidine: a theoretical and VCD spectroscopy study.

    PubMed

    Vargas, Angelo; Bonalumi, Norberto; Ferri, Davide; Baiker, Alfons

    2006-01-26

    The conformational analysis of the synthetic chiral modifier O-phenyl-cinchonidine (PhOCD) used in enantioselective hydrogenations over noble metal catalysts has been performed at a PM3 semiempirical level in vacuum. The minimum energy conformations calculated at the DFT level with a medium-size basis set have been compared to those of the parent alkaloid cinchonidine (CD). PhOCD behaves similarly to CD and shows four main conformers, denoted as Closed(1), Closed(2), Open(3), and Open(4). Open(3) is found to be the most stable in vacuum and in CH2Cl2 and CCl4 solvents. A comprehensive normal-mode analysis has been performed for these conformers, and assignment of the infrared spectrum of PhOCD in CCl4 (epsilon = 2.2) has been performed using the calculated spectrum of Open(3), which appears to be the most populated in this solvent. A combined theoretical-experimental VCD spectroscopy approach was used to increase the spectroscopic sensitivity toward changes in the distribution of conformers upon change of solvent polarity. The VCD spectra confirm that Open(3) is by far the most stable conformation in CCl4 (epsilon = 2.2) and indicate that an excess Closed(2) conformer has to be expected in CD2Cl2 (epsilon = 8.9). The possible influence of this conformational behavior is discussed on the basis of available catalytic data and in relation to the enantioselective potential of PhOCD as a chiral modifier on supported metal catalysts.

  19. Empirical Computation of IR and Vcd Spectra of RNA and Spectroscopic Analysis of the Tat-Tar Interaction.

    NASA Astrophysics Data System (ADS)

    Xiang, Ting

    In the first part of this thesis, we present models of VCD and IR intensities computation which are based on the exciton approach. The models include degenerate extended coupled oscillator model (DECO), nondegenerate extended oscillator model (NECO) and pseudo-single strand approach (PSS). We also show the necessity to include vibrations other than the C=O stretching motion and improve our computation by adjusting the direction of dipole derivative with respect to the C=O bond direction. We report observed and computed IR and VCD spectra of a number of polyribonucleic acids in D_2O/buffer solution in the 1600 -1750 cm^{-1}^ectral region. The experimental data are compared with results calculated using different levels of sophistication within the exciton approach. In the second part of this thesis, presented the CD, VCD, stopped-flow and molecular modeling results of a short peptide, which contains the basic region of the HIV-1 Tat (Trans-activator) protein, interacting with DeltaTAR, a shortened form of native TAR (Trans-activation response element) which is located at the 5^' end of the HIV long terminal repeat. The results confirm the conformational changes of both molecules upon binding to each other. Measured and computed VCD spectra suggest a left handed helix structure for the peptide. Kinetic studies indicate a two step mechanism for the binding reaction of these two molecules with k _1=0.7times10^8 { rm M}^{-1}{rm sec }^{-1} and rm k_2=69.4 sec^{-1}..

  20. Bioactive montanine derivatives from halide-induced rearrangements of haemanthamine-type alkaloids. Absolute configuration by VCD.

    PubMed

    Cedrón, Juan C; Estévez-Braun, Ana; Ravelo, Angel G; Gutiérrez, David; Flores, Ninoska; Bucio, María A; Pérez-Hernández, Nury; Joseph-Nathan, Pedro

    2009-04-01

    An unexpected rearrangement of haemanthamine-type alkaloids in the presence of halogenating agents has been found. Rearranged compounds present the 5,11-methanomorphantridine framework characteristic of montanine-type alkaloids. These compounds are difficult to obtain because of their scarcity in natural sources and because the synthetic approaches developed so far require numerous steps. Vibrational circular dichroism (VCD) spectroscopy was used to determine the absolute configuration of one of the rearranged compounds. Several rearranged alkaloids showed antimalarial activity.

  1. Theoretical Analysis of Vcd Spectra of α and β L-Fucopyranoside in the CH Stretching Region

    NASA Astrophysics Data System (ADS)

    Moussi, Sofiane; Ouamerali, Ourida

    2016-06-01

    Fucose is a deoxyhexose that is present in a wide variety of organisms. The stereochemical information, namely, glycosidic linkages α or β, gives significant features of the carbohydrate glycosidation position of the glycosylic acceptor [1]. Due to its applicability to all organic molecules and the reliability of ab initio quantum calculation, Vibrational Circular Dichroism VCD has some advantages over conventional electronic spectroscopy. However, for a molecule with many chiral centers such as carbohydrate, determination of the absolute configuration tends to be difficult because the information from each stereochemical center are mixed and averaged over the spectrum. T. Taniguchi et al [2] reported that in the CH stretching region of carbohydrate, methyl glycosides exhibit a characteristic VCD peak at 2840 wn, the sign solely reflects the anomeric carbon absolute configuration. This work is an investigation of theoretical VCD spectra of α-L-fucopyranoside and β-L-fucopyranoside with an implicit (PCM) and explicit consideration of water molecules using density functional theory DFT and the Potential Energy Distribution's analysis (PED). [1]. a) C.-H. Wong, Carbohydrate -Based Drug Discovery, Wiley-VCH Weinheinium 2003; b) T. Taniguchi, K. Monde, Wiley VCH Verlag GmbH§ Co. KGaA, Weinhein chem asian J. 2007, 2,1258-1266 [2]. T. Taniguchi et al. Tetrahedron Letters 45 (2004) 8451-8453

  2. Spectroscopic analysis, AIM, NLO and VCD investigations of acetaldehyde thiosemicarbazone using quantum mechanical simulations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Prabakar, P. C. Jobe; Ramalingam, S.; Govindarajan, M.; Gnanamuthu, S. Joshua; Pandian, G. V.

    2016-08-01

    The prepared Acetaldehyde thiosemicarbazone (ATSC) have been investigated by both the experimental and theoretical methods; through this work, the essentiality of elucidation of molecular fragments source linear and non-linear optical properties was explored. The stability of the structure and entire calculations have been performed on HF and B3LYP methods with 6-311++G(d,p) level of basis set. The Mulliken charge profile, electronic, optical and hyper polarizability analyses have been carried out in order to evaluate nonlinear optical (NLO) performance of the present compound. The exact optical location of the ATSC was determined by executing UV-Visible calculations on TDSCF method. The existence of the molecular group for the inducement and tuning of NLO properties were thoroughly investigated by performing fundamental vibrational investigation. The optical energy transformation among frontier molecular levels has been described in UV-Visible region. The Gibbs energy coefficient of thermodynamic functions was monitored in different temperature and it was found constant irrespective of temperatures. The appearance of different chemical environment of H and C was monitored from the 1H and 13C NMR spectra. The vibrational optical polarization characteristics with respect to molecular composition in the compound have been studied by VCD spectrum. The bond critical point, Laplacian of electron density, electron kinetic energy density and total electron energy density have calculated and analysed using AIM study.

  3. Structural analyses of experimental 13C edited amide I' IR and VCD for peptide β-sheet aggregates and fibrils using DFT-based spectral simulations.

    PubMed

    Welch, William R W; Keiderling, Timothy A; Kubelka, Jan

    2013-09-12

    In the preceding paper, computational models based on density functional theory (DFT) were presented to characterize the sensitivity of vibrational spectroscopic methods (IR, VCD, and Raman) to structural features of β-sheets. Isotopically edited amide I' IR for peptides labeled with (13)C in multiple different sites provides the most structurally distinct signatures of strand alignment, while VCD is sensitive to the sheet twist and intersheet stacking. In this report, we simulate the IR and VCD spectra for models approximating structures of four β-sheet forming peptides previously experimentally studied using these methods with (13)C isotopic editing. Various register alignments are tested. Agreement with experiment is evaluated based on frequency shifts of both the (12)C and (13)C IR amide I' signals, relative intensity patterns, and VCD spectra where available. While for the simulation of IR spectra canonical planar sheets provide a sufficient model system, for VCD simulation twisted, stacked sheets are required in order to reproduce strong couplet-like amide I' VCD. Effects of the solvent (water) and amino acid side chains are also tested by using a simplified, electrostatic solvent model and atomic partial charges for the side chains. Very good agreement with experimental spectra is obtained, particularly for the relative (12)C and (13)C band frequencies. All four peptide models are shown to be antiparallel as had previously been assumed. However, in some cases our simulations are consistent with different register alignment of strands than originally proposed.

  4. An assessment of anti-Müllerian hormone in predicting mating outcomes in female hamsters that have undergone natural and chemically-accelerated reproductive aging.

    PubMed

    Roosa, Kristen A; Zysling, Devin A; Place, Ned J

    2015-04-01

    In mammals, female fertility declines with age due in part to a progressive loss of ovarian follicles. The rate of follicle decline varies among individuals making it difficult to predict the age of onset of reproductive senescence. Serum anti-Müllerian hormone (AMH) concentrations correlate with the numbers of ovarian follicles, and therefore, AMH could be a useful predictor of female fertility. In women and some production animals, AMH is used to identify which individuals will respond best to ovarian stimulation for assisted reproductive technologies. However, few studies have evaluated AMH's predictive value in unassisted reproduction, and they have yielded conflicting results. To assess the predictive value of AMH in the context of reproductive aging, we prospectively measured serum AMH in 9-month-old Siberian hamsters shortly before breeding them. Female Siberian hamsters experience substantial declines in fertility and fecundity by 9months of age. We also measured serum AMH in 5-month-old females treated with 4-vinylcyclohexene diepoxide (VCD), which selectively destroys ovarian follicles and functionally accelerates ovarian aging. Vehicle-treated 5-month-old females served as controls. AMH concentrations were significantly reduced in VCD-treated females yet many females with low AMH reproduced successfully. On average, both young and old hamsters that littered had higher AMH concentrations than females that did not. However, some females with relatively high AMH concentrations failed to litter, whereas several with low AMH succeeded. Our results suggest that mean AMH concentration can predict mating outcomes on a population or group level, but on an individual basis, a single AMH determination is less informative.

  5. Life Testing of the Vapor Compression Distillation/Urine Processing Assembly (VCD/UPA) at the Marshall Space Flight Center (1993 to 1997)

    NASA Technical Reports Server (NTRS)

    Wieland, P.; Hutchens, C.; Long, D.; Salyer, B.

    1998-01-01

    Wastewater and urine generated on the International Space Station will be processed to recover pure water using vapor compression distillation (VCD). To verify the long-term reliability and performance of the VCD Urine Processor Assembly (UPA), life testing was performed at the Marshall Space Flight Center (MSFC) from January 1993 to April 1996. Two UPA'S, the VCD-5 and VCD-5A, were tested for 204 days and 665 days, respectively. The compressor gears and the distillation centrifuge drive belt were found to have operating lives of approximately 4,800 hours, equivalent to 3.9 years of operation on ISS for a crew of three at an average processing rate of 1.76 kg/h (3.97 lb/h). Precise alignment of the flex-splines of the fluids and purge pump motor drives is essential to avoid premature failure after about 400 hours of operation. Results indicate that, with some design and procedural modifications and suitable quality control, the required performance and operational life can be met with the VCD/UPA.

  6. A chiral rhenium complex with predicted high parity violation effects: synthesis, stereochemical characterization by VCD spectroscopy and quantum chemical calculations.

    PubMed

    Saleh, Nidal; Zrig, Samia; Roisnel, Thierry; Guy, Laure; Bast, Radovan; Saue, Trond; Darquié, Benoît; Crassous, Jeanne

    2013-07-14

    With their rich electronic, vibrational, rotational and hyperfine structure, molecular systems have the potential to play a decisive role in precision tests of fundamental physics. For example, electroweak nuclear interactions should cause small energy differences between the two enantiomers of chiral molecules, a signature of parity symmetry breaking. Enantioenriched oxorhenium(VII) complexes S-(-)- and R-(+)-3 bearing a chiral 2-methyl-1-thio-propanol ligand have been prepared as potential candidates for probing molecular parity violation effects via high resolution laser spectroscopy of the Re=O stretching. Although the rhenium atom is not a stereogenic centre in itself, experimental vibrational circular dichroism (VCD) spectra revealed a surrounding chiral environment, evidenced by the Re=O bond stretching mode signal. The calculated VCD spectrum of the R enantiomer confirmed the position of the sulfur atom cis to the methyl, as observed in the solid-state X-ray crystallographic structure, and showed the presence of two conformers of comparable stability. Relativistic quantum chemistry calculations indicate that the vibrational shift between enantiomers due to parity violation is above the target sensitivity of an ultra-high resolution infrared spectroscopy experiment under active preparation.

  7. Economic and environmental benefits of reducing standby power lossin DVD/VCD players and copiers in China

    SciTech Connect

    Lin, Jiang; Li, Tienan; Li, Aizhen; Zhang, Guoqing

    2004-06-01

    's certification activities. Media events organized by CECP have greatly improved the country's awareness of standby power loss. Reducing standby power loss has been formally incorporated into China's energy efficiency policy portfolio and in China's collaboration with the international community on the subject of energy efficiency (IEA, 2001). In phase II of the program, CECP's main task was to assess the market for DVD/VCD (Digital Versatile/Video Disc and Video Compact Disc) players and copiers to analyze the economic and technical benefits of energy conservation potential, and to develop technical specifications for DVD/VCD players and copiers, with technical assistance from LBNL. Having built on the success of Phase I, CECP paid great attention to the appraisal of market conditions and the economic and environmental benefits of reducing standby power loss in DVD/VCD players and copiers, and solicited inputs from stakeholders before finalizing the product certification requirements. This paper summarizes the expected energy conservation and environmental benefits due to the implementation of certification programs for DVD/VCD players and copiers in China.

  8. Simultaneous optical coherence tomography and laser induced fluorescence imaging in rat model of ovarian carcinogenesis

    PubMed Central

    Hariri, Lida P; Liebmann, Erica R; Marion, Samuel L; Hoyer, Patricia B; Davis, John R; Brewer, Molly A

    2010-01-01

    Determining if an ovarian mass is benign or malignant is an ongoing clinical challenge. The development of reliable animal models provides means to evaluate new diagnostic tools to more accurately determine if an ovary has benign or malignant features. Although sex cord-stromal tumors (SCST) account for 0.1–0.5% of ovarian malignancies, they have similar appearances to more aggressive epithelial cancers and can serve as a prototype for developing better diagnostic methods for ovarian cancer. Optical coherence tomography (OCT) and laser-induced fluorescence (LIF) spectroscopy are non-destructive optical imaging modalities. OCT provides architectural cross-sectional images at near histological resolutions and LIF provides biochemical information. We utilize combined OCT-LIF to image ovaries in post-menopausal ovarian carcinogenesis rat models, evaluating normal cyclic, acyclic and neoplastic ovaries. Eighty-three female Fisher rats were exposed to combinations of control sesame oil, 4-vinylcyclohexene diepoxide (VCD) to induce ovarian failure, and/or 7,12-dimethylbenz[a]anthracene (DMBA) to induce carcinogenesis. Three or five months post-treatment, 162 ovaries were harvested and imaged with OCT-LIF: 40 cyclic, 105 acyclic and 17 SCST. OCT identified various follicle stages, corpora lutea (CL), CL remnants, epithelial invaginations/inclusions and allowed for characterization of both cystic and solid SCST. Signal attenuation comparisons between CL and solid SCST revealed statistically significant increases in attenuation among CL. LIF characterized spectral differences in cyclic, acyclic and neoplastic ovaries attributed to collagen, NADH/FAD and hemoglobin absorption. We present combined OCT-LIF imaging in a rat ovarian carcinogenesis model, providing preliminary criteria for normal cyclic, acyclic and SCST ovaries which support the potential of OCT-LIF for ovarian imaging. PMID:21108515

  9. Vibrational, NMR and UV-Visible spectroscopic investigation, VCD and NLO studies on Benzophenone thiosemicarbazone using computational calculations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Jobe Prabakar, P. C.; Ramalingam, S.; Periandy, S.; Parasuraman, K.

    2016-04-01

    In order to explore the unbelievable NLO property of prepared Benzophenone thiosemicarbazone (BPTSC), the experimental and theoretical investigation has been made. The theoretical calculations were made using RHF and CAM-B3LYP methods at 6-311++G(d,p) basis set. The title compound contains Cdbnd S ligand which helps to improve the second harmonic generation (SHG) efficiency. The molecule has been examined in terms of the vibrational, electronic and optical properties. The entire molecular behavior was studied by their fundamental IR and Raman wavenumbers and was compared with the theoretical aspect. The molecular chirality has been studied by performing vibrational circular dichroism (circularly polarized infrared radiation). The Mulliken charge levels of the compound ensure the perturbation of atomic charges according to the ligand. The molecular interaction of frontier orbitals emphasizes the modification of chemical properties of the compound through the reaction path. The enormous amount of NLO activity was induced by the Benzophenone in thiosemicarbazone. The Gibbs free energy was evaluated at different temperature and from which the enhancement of chemical stability was stressed. The VCD spectrum was simulated and the optical dichroism of the compound has been analyzed.

  10. Identifying dominant conformations of N-acetyl-L-cysteine methyl ester and N-acetyl-L-cysteine in water: VCD signatures of the amide I and the Cdbnd O stretching bands

    NASA Astrophysics Data System (ADS)

    Poopari, Mohammad Reza; Dezhahang, Zahra; Xu, Yunjie

    2015-02-01

    Infrared (IR) and vibrational circular dichroism (VCD) spectra of N-Acetyl-L-Cysteine Methyl Ester (NALCME) and N-Acetyl-L-Cysteine (NALC) in D2O under different pHs were measured. We focus on the VCD signatures of the amide I and the Cdbnd O stretching spectral signatures of the neutral NALCME and NALC species and the related ones of the deprotonated NALC species in the region of 1800-1500 cm-1. A sign inversion is observed for the amide I VCD band going from the neutral NALCME and NALC to the deprotonated NALC species. Density functional theory (DFT) calculations were carried out to search for the possible conformations of these three species and to simulate their IR and VCD spectra at the B3LYP/aug-cc-pVTZ level in the gas phase and with the polarization continuum model of water solvent. The most stable conformations found for neutral NALCME and NALC exhibit drastically difference VCD patterns, whereas those of deprotonated NALC show similar patterns. We establish an empirical structural-spectral relationship where the aforementioned VCD signatures can be used as spectral markers to identify dominant conformations of these two amino acid derivatives under different pHs. It is recognized that the dominant conformers identified using the VCD spectral markers differ from those based on the relative DFT energies for neutral NALCME and NALC. The influence of solvent on both the conformational geometries and their relative stabilities is discussed. The aforementioned discrepancy can be attributed to the explicit solute-solvent hydrogen-bonding interactions which are not accounted for in the calculations. The empirical structural-spectral relationship identified can potentially be applied to large, related amino acids and polypeptides in water.

  11. The Self-aggregation of A Polyalanine Octamer Promoted by Its C-Terminal Tyrosine And Probed By A Strongly Enhanced VCD Signal

    PubMed Central

    Measey, Thomas J.; Smith, Kathryn B.; Decatur, Sean M.; Zhao, Liming; Yang, Guoliang; Schweitzer-Stenner, Reinhard

    2009-01-01

    The 8-residue alanine oligopeptide, Ac-A4KA2Y-NH2 (AKY8), was found to form amyloid-like fibrils upon incubation at room temperature in acidified aqueous solution, at peptide concentrations > 10 mM. The fibril solution exhibits an enhanced VCD couplet in the amide I’ band region, which is nearly 2 orders of magnitude larger than typical polypeptide/protein signals in this region. The UV-CD spectrum of the fibril solution shows circular dichroism in the region associated with the tyrosine side chain absorption. A similar peptide, Ac-A4KA2-NH2 (AK7), lacking in a terminal tyrosine residue, does not aggregate. These results suggest a pivotal role for the C-terminal tyrosine residue in stabilizing the aggregation state of this peptide. It is speculated that interactions between the lysine and tyrosine side chains of consecutive strands in an anti-parallel arrangement, e.g. via cation-π interactions, are responsible for the stabilization of the resulting fibrils. These results offer considerations and insight for the de novo design of self-assembling oligopeptides for biomedical and biotechnological applications, and highlight the usefulness of VCD as a tool to probe amyloid fibril formation. PMID:19958029

  12. The VCD method--a simple and reliable way to distinguish cage C and B atoms in (hetero)carborane structures determined crystallographically.

    PubMed

    McAnaw, Amelia; Scott, Greig; Elrick, Lisa; Rosair, Georgina M; Welch, Alan J

    2013-01-21

    Replacing a boron vertex in a [B(n)H(n)](2-) cluster with a smaller atom, e.g. carbon, results in the distance from that atom to the polyhedral centroid being shorter. This forms the basis of a simple but very effective method of distinguishing between B and C atoms in (hetero)carboranes that have been studied crystallographically, the Vertex-to-Centroid Distance (VCD) method. Examples of well-characterised icosahedral and sub-icosahedral closo carboranes, nido carboranes, icosahedral metallacarboranes and supraicosahedral metallacarboranes are used to illustrate the generality of the VCD method. In this process a number of structures are identified in which the method suggests B/C disorder not previously recognised and some structures in which it appears that a cage C atom has been wrongly assigned. The largest sub-group of heterocarboranes is the family of 3,1,2-MC(2)B(9) compounds, and for these species consideration of Exopolyhedral Ligand Orientation (ELO) can sometimes be used to quickly suggest when a literature structure is suspect in terms of cage C atom positioning. The crystal structure of one such compound, 3,3-NO(3)-3-PPh(3)-3,1,2-closo-RhC(2)B(9)H(11), has been redetermined and the correct location of the cage C atoms established.

  13. Bortezomib-cyclophosphamide-dexamethasone (VCD) versus bortezomib-thalidomide-dexamethasone (VTD) -based regimens as induction therapies in newly diagnosed transplant eligible patients with multiple myeloma: a meta-analysis.

    PubMed

    Leiba, Merav; Kedmi, Meirav; Duek, Adrian; Freidman, Tzachi; Weiss, Mia; Leiba, Ronit; Nagler, Arnon; Avigdor, Abraham

    2014-09-01

    Three-drug induction regimens have become the standard of care in newly diagnosed transplant-eligible multiple myeloma patients. Two frequently used protocols are bortezomib, cyclophosphamide and dexamethasone (VCD) and bortezomib, thalidomide and dexamethasone (VTD). Comparisons between the two are lacking. The present study aimed to identify the differences in response rate and toxicity between the two regimens. Databases were searched using the terms 'VTD' or 'VCD' and 'induction regimens for newly diagnosed multiple myeloma'. Prospective trials evaluating initial response in transplant eligible patients were included. The main outcome measures were response rates and adverse events. Eight clinical trials were eligible for analysis. Overall 672 patients were treated with either VCD (n = 157) or VTD (n = 515) as induction therapy. Patients treated with VTD presented with a significantly higher complete/near complete response (34% vs. 6%, P = 0·002) as well as a higher very good partial response rate or better, following induction therapy (62% vs. 27%, P < 0·0001). Although grade 3-4 neurotoxicity was more frequent during VTD therapy (11% vs. 6%, P = 0·057), a higher incidence of overall grade 3-4 adverse events was found in the VCD-treated patients (74% vs. 51%, P < 0·001). VTD induction therapy may be superior in achieving deeper response rate following induction therapy, and is better tolerated.

  14. Conformations of phenylalanine in the tripeptides AFA and GFG probed by combining MD simulations with NMR, FTIR, polarized Raman, and VCD spectroscopy.

    PubMed

    Pizzanelli, Silvia; Forte, Claudia; Monti, Susanna; Zandomeneghi, Giorgia; Hagarman, Andrew; Measey, Thomas J; Schweitzer-Stenner, Reinhard

    2010-03-25

    Conformational properties of small, flexible peptides are a matter of ongoing interest since they can be considered as models for unfolded proteins. However, the investigation of the conformations of small peptides is challenging as they are ensembles of rapidly interconverting conformers; moreover, the different methods used are prone to different approximations and errors. In order to obtain more reliable results, it is prudent to combine different techniques; here, molecular dynamics (MD) simulations together with nuclear magnetic resonance (NMR), Fourier transform IR (FTIR), polarized Raman, and vibrational circular dichroism (VCD) measurements were used to study the conformational propensity of phenylalanine in the tripeptides AFA and GFG, motivated by the relevance of phenylalanine for the self-aggregation of peptides. The results of this analysis indicate that the F residue predominantly populates the beta-strand (beta) and polyproline II (PPII) conformations in both AFA and GFG. However, while phenylalanine exhibits a propensity for beta-strand conformations in GFG (0.40 < or = beta population < or = 0.69 and 0.29 < or = PPII population < or = 0.42), the substitution of terminal glycines with alanine residues induces a higher population of PPII (0.31 < or = beta population < or = 0.50 and 0.37 < or = PPII population < or = 0.57).

  15. In vivo three-dimensional optical coherence tomography and multiphoton microscopy in a mouse model of ovarian neoplasia

    NASA Astrophysics Data System (ADS)

    Watson, Jennifer M.; Marion, Samuel L.; Rice, Photini Faith; Bentley, David L.; Besselsen, David; Utzinger, Urs; Hoyer, Patricia B.; Barton, Jennifer K.

    2013-03-01

    Our goal is to use optical coherence tomography (OCT) and multiphoton microscopy (MPM) to detect early tumor development in a mouse model of ovarian neoplasia. We hope to use information regarding early tumor development to create a diagnostic test for high-risk patients. In this study we collect in vivo images using OCT, second harmonic generation and two-photon excited fluorescence from non-vinylcyclohexene diepoxide (VCD)-dosed and VCD-dosed mice. VCD causes follicular apoptosis (simulating menopause) and leads to tumor development. Using OCT and MPM we visualized the ovarian microstructure and were able to see differences between non-VCD-dosed and VCD-dosed animals. This leads us to believe that OCT and MPM may be useful for detecting changes due to early tumor development.

  16. What Is Vocal Cord Dysfunction (VCD)?

    MedlinePlus

    ... your vocal cords. The breathing test is called spirometry and must include a flow-volume loop. This ... be so hard. To learn more about the spirometry test, see the ATS Patient Information Series fact ...

  17. Xenobiotic Effects on Ovarian Preantral Follicles1

    PubMed Central

    Mark-Kappeler, Connie J.; Hoyer, Patricia B.; Devine, Patrick J.

    2011-01-01

    Women are born with a finite population of ovarian follicles, which are slowly depleted during their reproductive years until reproductive failure (menopause) occurs. The rate of loss of primordial follicles is determined by genetic and environmental influences, but certain toxic exposures can accelerate this process. Ionizing radiation reduces preantral follicle numbers in rodents and humans in a dose-dependent manner. Cigarette smoking is linked to menopause occurring 1–4 yr earlier than with nonsmokers, and components of smoke, polycyclic aromatic hydrocarbons, can cause follicle depletion in rodents or in ovaries in vitro. Chemotherapeutic agents, such as alkylating drugs and cisplatin, also cause loss of preantral ovarian follicles. Effects depend on dose, type, and reactivity of the drug, and the age of the individual. Evidence suggests DNA damage may underlie follicle loss induced by one common alkylating drug, cyclophosphamide. Occupational exposures have also been linked to ovarian damage. In an industrial setting, 2-bromopropane caused infertility in men and women, and it can induce ovarian follicle depletion in rats. Solvents, such as butadiene, 4-vinylcyclohexene, and their diepoxides, can also cause specific preantral follicle depletion. The mechanism(s) underlying effects of the latter compound may involve alterations in apoptosis, survival factors such as KIT/Kit Ligand, and/or the cellular signaling that maintains primordial follicle dormancy. Estrogenic endocrine disruptors may alter follicle formation/development and impair fertility or normal development of offspring. Thus, specific exposures are known or suspected of detrimentally impacting preantral ovarian follicles, leading to early ovarian failure. PMID:21697514

  18. Design, fabrication and testing of a dual catalyst ammonia removal system for a urine VCD unit

    NASA Technical Reports Server (NTRS)

    Budinikas, P.

    1980-01-01

    A three-man capacity catalytic system for the recovery of water from urine was designed, constructed, and tested, it was designed to operate with feed streams containing high concentrations of urine vapor and only 5 to 7% of oxygen for the oxidation of ammonia and volatile organic vapor.It can operate either in a flow-through or a recycle mode and is capable of accepting the urine vapor produced by a vapor compression distillation evaporator. Testing consisted of short preliminary and optimization test, an endurance test of 74 hours continuous operation, and recycle tests using both air and oxygen. The system was designed for a urine processing rate of 0.86 liters/hr; however, it was tested at rates up to 1.2 liter/hr. Untreated urine evaporated by an electrically heated evaporator was used. The quality of the recovered water meets the U.S. Drinking Water Standards, with the exception of a low pH. Accumulation of solids in the urine sludge is reduced to approximately 65% of the anticipated value.

  19. Analysis of butadiene monoepoxide and butadiene diepoxide in various tissues of sprague-dawley rats and B6C3F{sub 1} mice following low-level exposures to 1,3-butadiene

    SciTech Connect

    Thornton-Manning, J.R.; Bechtold, W.E.; Dahl, A.R.; Henderson, R.F.

    1994-11-01

    1,3-Butadiene (BD) is used extensively in the production of styrene-butadiene rubber, polybutadiene elastomers, and other polymers. Occupational exposures of workers in areas with concentrations of up to 374 ppm BD have been documented in U.S. plants. Additionally, BD is present in cigarette smoke, gasoline vapors, and automobile exhaust resulting in exposures of this chemical to most of the U.S. population. Epidemiological studies have revealed increased incidences of mortality due to lymphatic and hematopoietic cancers among rubber industry workers exposed to BD. However, because these workers were most likely exposed to a wide variety of potentially harmful compounds, the contribution of BD to increased carcinogenic risk is uncertain. The purpose of the present investigation was to examine the production and disposition of BDO and BDO{sub 2} in several target tissues in rats and mice during and following 4-h exposures to a low-level (62.5 ppm) of BD.

  20. Comparison of bioavailable vanadium in alfalfa rhizosphere soil extracted by an improved BCR procedure and EDTA, HCl, and NaNO₃ single extractions in a pot experiment with V-Cd treatments.

    PubMed

    Yang, Jie; Teng, Yanguo; Zuo, Rui; Song, Liuting

    2015-06-01

    The BCR sequential extraction procedure was compared with EDTA, HCl, and NaNO3 single extractions for evaluating vanadium bioavailability in alfalfa rhizosphere soil. The amounts of vanadium extracted by these methods were in the following order: BCR (bioavailable V) > EDTA ≈ HCl > NaNO3. Both correlation analysis and stepwise regression were adopted to illustrate the extractable vanadium between different reagents. The correlation coefficients between extracted vanadium and the vanadium contents in alfalfa roots were R NaNO3 = 0.948, R HCl = 0.902, R EDTA = 0.816, and R bioavailable V = 0.819. The stepwise multiple regression equation of the NaNO3 extraction was the most significant at a 95 % confidence interval. The influence of pH, total organic carbon, and cadmium content of soil to vanadium bioavailability were not definite. In summary, both the BCR sequential extraction and the single extraction methods were valid approaches for predicting vanadium bioavailability in alfalfa rhizosphere soil, especially the single extractions.

  1. Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization.

    PubMed

    Domingos, Sérgio R; Hartl, František; Buma, Wybren Jan; Woutersen, Sander

    2015-11-16

    Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.

  2. Quantum-cascade laser-based vibrational circular dichroism.

    PubMed

    Lüdeke, Steffen; Pfeifer, Marcel; Fischer, Peer

    2011-04-20

    Vibrational circular dichroism (VCD) spectra were recorded with a tunable external-cavity quantum-cascade laser (QCL). In comparison with standard thermal light sources in the IR, QCLs provide orders of magnitude more power and are therefore promising for VCD studies in strongly absorbing solvents. The brightness of this novel light source is demonstrated with VCD and IR absorption measurements of a number of compounds, including proline in water.

  3. New ru(II) complexes containing oxazoline ligands as epoxidation catalysts. Influence of the substituents on the catalytic performance.

    PubMed

    Serrano, Isabel; López, M Isabel; Ferrer, Íngrid; Poater, Albert; Parella, Teodor; Fontrodona, Xavier; Solà, Miquel; Llobet, Antoni; Rodríguez, Montserrat; Romero, Isabel

    2011-07-01

    The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [Ru(II)(T)(D)(X)](n+) (T = trispyrazolylmethane (tpm); D = ((4S,4'S)-(-)-4,4',5,5'-tetrahydro-4,4'-bis(1-methylethyl)-2,2'-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H(2)O) has been described. All complexes have been spectroscopically characterized in solution through (1)H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH(2) complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru(II)(R-box-C)(tpm)OH(2)](BF(4))(2), R = Bz, 3'c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3'c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as

  4. Vapor Compression Distillation Urine Processor Lessons Learned from Development and Life Testing

    NASA Technical Reports Server (NTRS)

    Hutchens, Cindy F.; Long, David A.

    1999-01-01

    Vapor Compression Distillation (VCD) is the chosen technology for urine processing aboard the International Space Station (155). Development and life testing over the past several years have brought to the forefront problems and solutions for the VCD technology. Testing between 1992 and 1998 has been instrumental in developing estimates of hardware life and reliability. It has also helped improve the hardware design in ways that either correct existing problems or enhance the existing design of the hardware. The testing has increased the confidence in the VCD technology and reduced technical and programmatic risks. This paper summarizes the test results and changes that have been made to the VCD design.

  5. Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

    NASA Astrophysics Data System (ADS)

    Poater, Albert; Falivene, Laura; Cavallo, Luigi; Llobet, Antoni; Rodríguez, Montserrat; Romero, Isabel; Solà, Miquel

    2013-07-01

    The reactivity of a new family of complexes with general formula [RuIV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands.

  6. Ovarian toxicity and carcinogenicity in eight recent national toxicology program studies

    SciTech Connect

    Maronpot, R.R.

    1987-08-01

    Ovarian toxicity and/or carcinogenicity has been documented for at least eight chemicals recently tested in National Toxicity Program prechronic and chronic rodent studies. The chemicals that yielded treatment-related ovarian lesions were 1,3-butadiene, 4-vinylcyclohexene, vinylcylohexene deipoxide, nitrofurantoin, nitrofurazone, benzene, ..delta..-9-tetrahydrocannabinol, and tricresylphosphate. Typical nonneoplastic ovarian changes included hypoplasia, atrophy, follicular necrosis, and tubular hyperplasia. The most commonly observed treatment-related neoplasms were granulosa cell tumors and benign mixed tumors. A relationship between antecedent ovarian hypoplasia, atrophy, and hyperplasia and subsequent ovarian neoplasia is supported by some of these National Toxicology Program studies. Pathologic changes in other tissues such as the adrenal glands and uterus were associated with the treatment-related ovarian changes.

  7. Impact of environmental exposures on ovarian function and role of xenobiotic metabolism during ovotoxicity

    PubMed Central

    Bhattacharya, Poulomi; Keating, Aileen F.

    2012-01-01

    The mammalian ovary is a heterogeneous organ, and contains oocyte-containing follicles at varying stages of development. The most immature follicular stage, the primordial follicle, comprises the ovarian reserve and is a finite number, defined at the time of birth. Depletion of all follicles within the ovary leads to reproductive senescence, known as menopause. A number of chemical classes can destroy follicles thus hastening entry into the menopausal state. The ovarian response to chemical exposure can determine the extent of ovotoxicity that occurs. Enzymes capable of bioactivating as well as detoxifying xenobiotics are expressed in the ovary and their impact on ovotoxicity have been partially characterized for trichloroethylene, 7,12-dimethylbenz[a]anthracene, and 4-vinylcyclohexene. This review will discuss those studies, as well as illustrate where knowledge gaps remain for chemicals that have also been established as ovotoxicants. PMID:22531813

  8. Flexible moldable conductive current-limiting materials

    SciTech Connect

    Shea, John Joseph; Djordjevic, Miomir B.; Hanna, William Kingston

    2002-01-01

    A current limiting PTC device (10) has two electrodes (14) with a thin film of electric conducting polymer material (20) disposed between the electrodes, the polymer material (20) having superior flexibility and short circuit performance, where the polymer material contains short chain aliphatic diepoxide, conductive filler particles, curing agent, and, preferably, a minor amount of bisphenol A epoxy resin.

  9. Preparation and Characterization of Macro- & Monomers for Azide & Alkyne Cycloaddition Polyerization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In 1970 Robert Harper and colleagues, showed that poly(ethylene oxide)s and Poly(propylene oxide)s (PEOs and PPOs, respectively) are effective softeners for cotton fabrics (Textile Chemist and Colorist, 1970, 2(1), 37-41. Using this information, we developed PEO and PPO dibromides and diepoxides to ...

  10. Vulval Crohn's disease: a clinical study of 22 patients.

    PubMed

    Laftah, Zainab; Bailey, Clare; Zaheri, Shirin; Setterfield, Jane; Fuller, Lucinda Claire; Lewis, Fiona

    2015-04-01

    Vulval Crohn's disease [VCD] is a challenging condition that can occur without gastrointestinal Crohn's disease [GCD]. We reviewed the clinical features and effects of therapy in a cohort of 22 patients with VCD to determine whether the presence of GCD affected the clinical presentation and treatment response. Of these, 64% had GCD and 65% of these presented with GCD prior to VCD. Fissuring, ulceration, and scarring were more common in those with VCD alone. Potent and ultra-potent topical steroids showed benefit in most patients. There was no clear evidence of sustained remission with metronidazole. Azathioprine was the most commonly used oral immunosuppressive agent, with an efficacy of 57%. Patients with both VCD and GCD had a better clinical response compared with those with VCD alone [70% and 25%, respectively]. Infliximab and adalimumab were effective in 56% and 71% of patients, respectively. Excision of redundant tissue was helpful in four patients. The absence of GCD may delay the diagnosis in women who present with vulval symptoms alone. The more active clinical features in those with VCD alone may represent a more aggressive condition, or the severity of the cutaneous disease may have been reduced by immunosuppression taken for GCD. Several patients obtained sustained remission in their GCD with anti-tumor necrosis factor alpha [anti-TNFα] agents while the VCD remained active.

  11. A novel computational method for comparing vibrational circular dichroism spectra.

    PubMed

    Shen, Jian; Zhu, Chengyue; Reiling, Stephan; Vaz, Roy

    2010-08-01

    A novel method, SimIR/VCD, for comparing experimental and calculated VCD (vibrational circular dichroism) spectra is developed, based on newly defined spectra similarities. With computationally optimized frequency scaling and shifting, a calculated spectrum can be easily identified to match an observed spectrum, which leads to an unbiased molecular chirality assignment. The time-consuming manual band-fitting work is greatly reduced. With (1S)-(-)-alpha-pinene as an example, it demonstrates that the calculated VCD similarity is correlated with VCD spectra matching quality and has enough sensitivity to identify variations in the spectra. The study also compares spectra calculated using different DFT methods and basis sets. Using this method should facilitate the spectra matching, reduce human error and provide a confidence measure in the chiral assignment using VCD spectroscopy.

  12. Absolute configuration and predominant conformations of a chiral crown ether-based colorimetric sensor: a vibrational circular dichroism spectroscopy and DFT study of chiral recognition.

    PubMed

    Merten, Christian; Hyun, Myung Ho; Xu, Yunjie

    2013-05-01

    In the present work, we report a comprehensive vibrational circular dichroism (VCD) spectroscopic study of a chiral crown ether which features an axial chiral 3.3'-diphenyl-1,1'-binaphthyl group as chiral moiety. By comparing the experimental and calculated VCD spectra, we show that the presumably very flexible crown ether preferably adopts only one ring conformation. Conformational flexibility is observed in the 2,4-dinitrophenyl-diazophenol group, which was previously introduced for colorimetric detection of primary amines and amino alcohols (Cho et al., Chirality 2011;23:349-353). The VCD spectra of the host-guest complexes with phenyl glycinol (PG) and phenyl alaninol have been studied as well. Based on the spectra calculated, it is shown that the diastereomeric complexes in general can be differentiated using VCD spectroscopy. Furthermore, the experimental VCD spectra of the complexes of the host molecule with PG support the above finding.

  13. Reaction monitoring using mid-infrared laser-based vibrational circular dichroism.

    PubMed

    Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen

    2014-09-01

    Changes in vibrational circular dichroism (VCD) were recorded on-line during a chemical reaction. The chiral complex nickel-(-)-sparteine chloride was hydrolyzed to free (-)-sparteine base in a biphasic system of sodium hydroxide solution and chloroform (CHCl(3)). Infrared (IR) and VCD spectra were iteratively recorded after pumping a sample from the CHCl(3) phase through a lab-built VCD spectrometer equipped with a tunable mid-IR quantum cascade laser light source, which allows for VCD measurements even in the presence of strongly absorbing backgrounds. Time-dependent VCD spectra were analyzed by singular value decomposition and global exponential fitting. Spectral features corresponding to the complex and free (-)-sparteine could be clearly identified in the fitted amplitude spectrum, which was associated with an exponential decay with an apparent time constant of 127 min (t(½) = 88 min).

  14. Absolute configuration and predominant conformations of a chiral crown ether-based colorimetric sensor: a vibrational circular dichroism spectroscopy and DFT study of chiral recognition.

    PubMed

    Merten, Christian; Hyun, Myung Ho; Xu, Yunjie

    2013-05-01

    In the present work, we report a comprehensive vibrational circular dichroism (VCD) spectroscopic study of a chiral crown ether which features an axial chiral 3.3'-diphenyl-1,1'-binaphthyl group as chiral moiety. By comparing the experimental and calculated VCD spectra, we show that the presumably very flexible crown ether preferably adopts only one ring conformation. Conformational flexibility is observed in the 2,4-dinitrophenyl-diazophenol group, which was previously introduced for colorimetric detection of primary amines and amino alcohols (Cho et al., Chirality 2011;23:349-353). The VCD spectra of the host-guest complexes with phenyl glycinol (PG) and phenyl alaninol have been studied as well. Based on the spectra calculated, it is shown that the diastereomeric complexes in general can be differentiated using VCD spectroscopy. Furthermore, the experimental VCD spectra of the complexes of the host molecule with PG support the above finding. PMID:23620265

  15. Analysis of vibrational circular dichroism spectra of (s)-(+)-2-butanol by rotational strengths expressed in local symmetry coordinates.

    PubMed

    Shin, Saeko; Nakata, Munetaka; Hamada, Yoshiaki

    2006-02-16

    The vibrational circular dichroism (VCD) spectra of (S)-(+)-2-butanol have been observed in dilute CS(2) solutions. Two strong VCD bands are assigned mainly to the OH bending modes with the aid of quantum chemical calculations. The calculated VCD spectra corresponding to these bands are shown to depend on the conformation of the OH group. To understand this feature, we have calculated the contribution of each local vibrational mode to the rotational strengths and concluded that the coupling of the group vibrations between the in-plane and out-of-plane modes about the locally assumed symmetry planes play a significant role in VCD. This finding has provided a new scope of VCD in relation to molecular vibrations.

  16. Software-Assisted Depth Analysis of Optic Nerve Stereoscopic Images in Telemedicine.

    PubMed

    Xia, Tian; Patel, Shriji N; Szirth, Ben C; Kolomeyer, Anton M; Khouri, Albert S

    2016-01-01

    Background. Software guided optic nerve assessment can assist in process automation and reduce interobserver disagreement. We tested depth analysis software (DAS) in assessing optic nerve cup-to-disc ratio (VCD) from stereoscopic optic nerve images (SONI) of normal eyes. Methods. In a prospective study, simultaneous SONI from normal subjects were collected during telemedicine screenings using a Kowa 3Wx nonmydriatic simultaneous stereoscopic retinal camera (Tokyo, Japan). VCD was determined from SONI pairs and proprietary pixel DAS (Kowa Inc., Tokyo, Japan) after disc and cup contour line placement. A nonstereoscopic VCD was determined using the right channel of a stereo pair. Mean, standard deviation, t-test, and the intraclass correlation coefficient (ICCC) were calculated. Results. 32 patients had mean age of 40 ± 14 years. Mean VCD on SONI was 0.36 ± 0.09, with DAS 0.38 ± 0.08, and with nonstereoscopic 0.29 ± 0.12. The difference between stereoscopic and DAS assisted was not significant (p = 0.45). ICCC showed agreement between stereoscopic and software VCD assessment. Mean VCD difference was significant between nonstereoscopic and stereoscopic (p < 0.05) and nonstereoscopic and DAS (p < 0.005) recordings. Conclusions. DAS successfully assessed SONI and showed a high degree of correlation to physician-determined stereoscopic VCD. PMID:27190507

  17. The amide III vibrational circular dichroism band as a probe to detect conformational preferences of alanine dipeptide in water.

    PubMed

    Mirtič, Andreja; Merzel, Franci; Grdadolnik, Jože

    2014-07-01

    The conformational preferences of blocked alanine dipeptide (ADP), Ac-Ala-NHMe, in aqueous solution were studied using vibrational circular dichroism (VCD) together with density functional theory (DFT) calculations. DFT calculations of three most representative conformations of ADP surrounded by six explicit water molecules immersed in a dielectric continuum have proven high sensitivity of amide III VCD band shape that is characteristic for each conformation of the peptide backbone. The polyproline II (PII ) and αR conformation of ADP are associated with a positive VCD band while β conformation has a negative VCD band in amide III region. Knowing this spectral characteristic of each conformation allows us to assign the experimental amide III VCD spectrum of ADP. Moreover, the amide III region of the VCD spectrum was used to determine the relative populations of conformations of ADP in water. Based on the interpretation of the amide III region of VCD spectrum we have shown that dominant conformation of ADP in water is PII which is stabilized by hydrogen bonded water molecules between CO and NH groups on the peptide backbone.

  18. Vibrational Circular Dichroism Spectra for Large Molecules through Molecules-in-Molecules Fragment-Based Approach.

    PubMed

    Jose, K V Jovan; Beckett, Daniel; Raghavachari, Krishnan

    2015-09-01

    We present the first implementation of the vibrational circular dichroism (VCD) spectrum of large molecules through the Molecules-in-Molecules (MIM) fragment-based method. An efficient projection of the relevant higher energy derivatives from smaller fragments to the parent molecule enables the extension of the MIM method for the evaluation of VCD spectra (MIM-VCD). The overlapping primary subsystems in this work are constructed from interacting fragments using a number-based scheme and the dangling bonds are saturated with link hydrogen atoms. Independent fragment calculations are performed to evaluate the energies, Hessian matrix, atomic polar tensor (APT), and the atomic axial tensor (AAT). Subsequently, the link atom tensor components are projected back onto the corresponding host and supporting atoms through the Jacobian projection method, as in the ONIOM approach. In the two-layer model, the long-range interactions between fragments are accounted for using a less computationally intensive lower level of theory. The performance of the MIM model is calibrated on the d- and l-enantiomers of 10 carbohydrate benchmark molecules, with strong intramolecular interactions. The vibrational frequencies and VCD intensities are accurately reproduced relative to the full, unfragmented, results for these systems. In addition, the MIM-VCD method is employed to predict the VCD spectra of perhydrotriphenylene and cryptophane-A, yielding spectra in agreement with experiment. The accuracy and performance of the benchmark systems validate the MIM-VCD model for exploring vibrational circular dichroism spectra of large molecules.

  19. Software-Assisted Depth Analysis of Optic Nerve Stereoscopic Images in Telemedicine

    PubMed Central

    Xia, Tian; Patel, Shriji N.; Szirth, Ben C.

    2016-01-01

    Background. Software guided optic nerve assessment can assist in process automation and reduce interobserver disagreement. We tested depth analysis software (DAS) in assessing optic nerve cup-to-disc ratio (VCD) from stereoscopic optic nerve images (SONI) of normal eyes. Methods. In a prospective study, simultaneous SONI from normal subjects were collected during telemedicine screenings using a Kowa 3Wx nonmydriatic simultaneous stereoscopic retinal camera (Tokyo, Japan). VCD was determined from SONI pairs and proprietary pixel DAS (Kowa Inc., Tokyo, Japan) after disc and cup contour line placement. A nonstereoscopic VCD was determined using the right channel of a stereo pair. Mean, standard deviation, t-test, and the intraclass correlation coefficient (ICCC) were calculated. Results. 32 patients had mean age of 40 ± 14 years. Mean VCD on SONI was 0.36 ± 0.09, with DAS 0.38 ± 0.08, and with nonstereoscopic 0.29 ± 0.12. The difference between stereoscopic and DAS assisted was not significant (p = 0.45). ICCC showed agreement between stereoscopic and software VCD assessment. Mean VCD difference was significant between nonstereoscopic and stereoscopic (p < 0.05) and nonstereoscopic and DAS (p < 0.005) recordings. Conclusions. DAS successfully assessed SONI and showed a high degree of correlation to physician-determined stereoscopic VCD. PMID:27190507

  20. Calculation of the High-Temperature Point Defects Structure in Te-Rich CdTe

    NASA Astrophysics Data System (ADS)

    Dai, Shujun; Wang, Tao; Liu, Huimin; He, Yihui; Jie, Wanqi

    2016-06-01

    A thermodynamic equilibrium model for CdTe annealed under Te vapor is established, in which possible point defects and a defect reaction existing in undoped and In-doped Te-rich CdTe crystals are taken into consideration. Independent point defects, such as VCd, Cdi, and Tei, as well as defect complexes, namely TeCd-VCd (B complex), {{Te}}_{{Cd}}^{2 + } - {{V}}_{{Cd}}^{2 - } (D complex), {{In}}_{{Cd}}^{ + } - {{V}}_{{Cd}}^{ - } (A-center) and Tei-VCd (TeCd), are discussed based on the defect chemistry theory. More specially, the mass action law and quasi-chemical equations are used to calculate defects concentration and Fermi level in undoped and doped CdTe crystals with different indium concentrations. It is found that the Fermi level is controlled by a {{V}}_{{Cd}}^{2 - } , TeCd, and B/D-complex in undoped crystal. The concentration of VCd drops down in an obvious manner and that of TeCd rises for doped crystal with increasing [In].

  1. Calculation of the High-Temperature Point Defects Structure in Te-Rich CdTe

    NASA Astrophysics Data System (ADS)

    Dai, Shujun; Wang, Tao; Liu, Huimin; He, Yihui; Jie, Wanqi

    2016-10-01

    A thermodynamic equilibrium model for CdTe annealed under Te vapor is established, in which possible point defects and a defect reaction existing in undoped and In-doped Te-rich CdTe crystals are taken into consideration. Independent point defects, such as VCd, Cdi, and Tei, as well as defect complexes, namely TeCd-VCd (B complex), {Te}_{{Cd}}^{2 + } - {V}_{{Cd}}^{2 - } (D complex), {In}_{{Cd}}^{ + } - {V}_{{Cd}}^{ - } (A-center) and Tei-VCd (TeCd), are discussed based on the defect chemistry theory. More specially, the mass action law and quasi-chemical equations are used to calculate defects concentration and Fermi level in undoped and doped CdTe crystals with different indium concentrations. It is found that the Fermi level is controlled by a {V}_{{Cd}}^{2 - } , TeCd, and B/D-complex in undoped crystal. The concentration of VCd drops down in an obvious manner and that of TeCd rises for doped crystal with increasing [In].

  2. Repositioning of Verrucosidin, a purported inhibitor of chaperone protein GRP78, as an inhibitor of mitochondrial electron transport chain complex I.

    PubMed

    Thomas, Simmy; Sharma, Natasha; Gonzalez, Reyna; Pao, Peng-Wen; Hofman, Florence M; Chen, Thomas C; Louie, Stan G; Pirrung, Michael C; Schönthal, Axel H

    2013-01-01

    Verrucosidin (VCD) belongs to a group of fungal metabolites that were identified in screening programs to detect molecules that preferentially kill cancer cells under glucose-deprived conditions. Its mode of action was proposed to involve inhibition of increased GRP78 (glucose regulated protein 78) expression during hypoglycemia. Because GRP78 plays an important role in tumorigenesis, inhibitors such as VCD might harbor cancer therapeutic potential. We therefore sought to characterize VCD's anticancer activity in vitro. Triple-negative breast cancer cell lines MDA-MB-231 and MDA-MB-468 were treated with VCD under different conditions known to trigger increased expression of GRP78, and a variety of cellular processes were analyzed. We show that VCD was highly cytotoxic only under hypoglycemic conditions, but not in the presence of normal glucose levels, and VCD blocked GRP78 expression only when glycolysis was impaired (due to hypoglycemia or the presence of the glycolysis inhibitor 2-deoxyglucose), but not when GRP78 was induced by other means (hypoxia, thapsigargin, tunicamycin). However, VCD's strictly hypoglycemia-specific toxicity was not due to the inhibition of GRP78. Rather, VCD blocked mitochondrial energy production via inhibition of complex I of the electron transport chain. As a result, cellular ATP levels were quickly depleted under hypoglycemic conditions, and common cellular functions, including general protein synthesis, deteriorated and resulted in cell death. Altogether, our study identifies mitochondria as the primary target of VCD. The possibility that other purported GRP78 inhibitors (arctigenin, biguanides, deoxyverrucosidin, efrapeptin, JBIR, piericidin, prunustatin, pyrvinium, rottlerin, valinomycin, versipelostatin) might act in a similar GRP78-independent fashion will be discussed. PMID:23755268

  3. Assignment of absolute stereostructures through quantum mechanics electronic and vibrational circular dichroism calculations.

    PubMed

    Dai, Peng; Jiang, Nan; Tan, Ren-Xiang

    2016-01-01

    Elucidation of absolute configuration of chiral molecules including structurally complex natural products remains a challenging problem in organic chemistry. A reliable method for assigning the absolute stereostructure is to combine the experimental circular dichroism (CD) techniques such as electronic and vibrational CD (ECD and VCD), with quantum mechanics (QM) ECD and VCD calculations. The traditional QM methods as well as their continuing developments make them more applicable with accuracy. Taking some chiral natural products with diverse conformations as examples, this review describes the basic concepts and new developments of QM approaches for ECD and VCD calculations in solution and solid states.

  4. Farnesyloxycoumarins, a new class of squalene-hopene cyclase inhibitors.

    PubMed

    Cravotto, Giancarlo; Balliano, Gianni; Robaldo, Bruna; Oliaro-Bosso, Simonetta; Chimichi, Stefano; Boccalini, Marco

    2004-04-19

    A few naturally occurring prenyl- and prenyloxycoumarins and several new related synthetic derivatives were evaluated as inhibitors of squalene-hopene cyclase (SHC), a useful model enzyme, to predict their interactions with oxidosqualene cyclase (OSC). Umbelliprenin-10',11'-monoepoxide (IC(50) 2.5 microM) and the corresponding 6',7'-10',11' diepoxide (IC(50) 1.5 microM) were the most active enzyme inhibitors.

  5. A Single Chiroptical Spectroscopic Method May Not Be Able To Establish the Absolute Configurations of Diastereomers: Dimethylesters of Hibiscus and Garcinia Acids

    PubMed Central

    Polavarapu, Prasad L.; Donahue, Emily A.; Shanmugam, Ganesh; Scalmani, Giovanni; Hawkins, Edward K.; Rizzo, Carmelo; Ibnusaud, Ibrahim; Thomas, Grace; Habel, Deenamma; Sebastian, Dellamol

    2013-01-01

    Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis. PMID:21568330

  6. A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids.

    PubMed

    Polavarapu, Prasad L; Donahue, Emily A; Shanmugam, Ganesh; Scalmani, Giovanni; Hawkins, Edward K; Rizzo, Carmelo; Ibnusaud, Ibrahim; Thomas, Grace; Habel, Deenamma; Sebastian, Dellamol

    2011-06-01

    Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis. PMID:21568330

  7. Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: a vibrational circular dichroism study of glycidol in water.

    PubMed

    Yang, Guochun; Xu, Yunjie

    2009-04-28

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of (S)-(-)-glycidol were measured in water with a concentration of 6.0M in the 1000-1750 cm(-1) region. Prominent and complex VCD spectral features were detected at the water bending vibrational region. Our experimental results show that water molecules can become optically active through hydrogen bonding interactions with glycidol molecules. To model the glycidol-water hydrogen bonding network in the solution, molecular dynamics simulations using the AMBER9 suite of programs were carried out. Altogether, 34 conformers of the small glycidol-(water)(N) clusters with N=1, 2, 3, and 4 were considered. Geometry optimizations, harmonic frequency calculations, and the VA and VCD intensity predictions of these small glycidol-water clusters were performed at the B3LYP/6-311++G(d,p) level of theory using the GAUSSIAN 03 program package. Strong cooperative hydrogen bonding effects were detected in the larger glycidol-(water)(N) clusters. The population weighted VA and VCD spectra of each N group of glycidol (water)(N=1,2,3,4) were used to produce the simulated VA and VCD spectra, which are in good agreement with the experimental VA and VCD spectra. The study shows that all these clusters make important contributions to the observed spectra and are the most important species in the aqueous solution with complicated equilibriums among them.

  8. Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: A vibrational circular dichroism study of glycidol in water

    NASA Astrophysics Data System (ADS)

    Yang, Guochun; Xu, Yunjie

    2009-04-01

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of (S)-(-)-glycidol were measured in water with a concentration of 6.0M in the 1000-1750 cm-1 region. Prominent and complex VCD spectral features were detected at the water bending vibrational region. Our experimental results show that water molecules can become optically active through hydrogen bonding interactions with glycidol molecules. To model the glycidol-water hydrogen bonding network in the solution, molecular dynamics simulations using the AMBER9 suite of programs were carried out. Altogether, 34 conformers of the small glycidol-(water)N clusters with N =1, 2, 3, and 4 were considered. Geometry optimizations, harmonic frequency calculations, and the VA and VCD intensity predictions of these small glycidol-water clusters were performed at the B3LYP/6-311++G(d,p) level of theory using the GAUSSIAN 03 program package. Strong cooperative hydrogen bonding effects were detected in the larger glycidol-(water)N clusters. The population weighted VA and VCD spectra of each N group of glycidol (water)N=1,2,3,4 were used to produce the simulated VA and VCD spectra, which are in good agreement with the experimental VA and VCD spectra. The study shows that all these clusters make important contributions to the observed spectra and are the most important species in the aqueous solution with complicated equilibriums among them.

  9. Studies of radiation-produced radicals and radical ions. Progress report, September 1, 1990--October 15, 1991

    SciTech Connect

    Williams, T.F.

    1991-12-31

    The radiolytic oxidation of anti-5-methylbicyclo[2.1.0]pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo[3.2.1]oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo[3.2.0]hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.

  10. Studies of radiation-produced radicals and radical ions

    SciTech Connect

    Williams, T.F.

    1991-01-01

    The radiolytic oxidation of anti-5-methylbicyclo(2.1.0)pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo(3.2.1)oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo(3.2.0)hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.

  11. Treatment of an industrial stream containing vinylcyclohexene by the H2O2/UV process.

    PubMed

    Gonçalves, Lenise V F; Azevedo, Eduardo B; de Aquino-Neto, Francisco R; Bila, Daniele M; Sant'Anna, Geraldo L; Dezotti, Márcia

    2016-10-01

    Petrochemical industries generate wastewaters containing pollutants that can severely impact the biological treatment systems. Some streams from specific production units may contain nonbiodegradable or toxic compounds that impair the performance of the wastewater treatment plant and should be segregated and treated by specific techniques. In this work, the utilization of chemical oxidation (H2O2/UV) was investigated for removing 4-vinylcyclohexene (VCH) from a liquid stream coming from the production of hydroxylated liquid polybutadiene (HLPB). Besides VCH, this stream also contains ethanol, hydrogen peroxide, and many other organic compounds. Experiments were carried out in a small-scale photochemical reactor (0.7 L) using a 25-W low-pressure mercury vapor lamp. The photochemical reactor was operated in batch, and the reaction times were comprised between 10 and 60 min. Assays were also performed with a synthetic medium containing VCH, H2O2, and ethanol to investigate the removal of these substances in a less complex aqueous matrix. By-products formed in the reaction were identified by gas chromatography and mass spectroscopy (GC-MS). VCH was significantly removed by the oxidation process, in most assays to undetectable levels. Ethanol removal varied from 16 to 23 % depending on the reaction conditions. Acetic acid, acetaldehyde, and diols were detected as by-products of the industrial wastewater stream oxidation. A drop on the toxicity of the industrial stream was also observed in assays using the organism Artemia salina. PMID:27392628

  12. Impact of environmental exposures on ovarian function and role of xenobiotic metabolism during ovotoxicity

    SciTech Connect

    Bhattacharya, Poulomi; Keating, Aileen F.

    2012-06-15

    The mammalian ovary is a heterogeneous organ and contains oocyte-containing follicles at varying stages of development. The most immature follicular stage, the primordial follicle, comprises the ovarian reserve and is a finite number, defined at the time of birth. Depletion of all follicles within the ovary leads to reproductive senescence, known as menopause. A number of chemical classes can destroy follicles, thus hastening entry into the menopausal state. The ovarian response to chemical exposure can determine the extent of ovotoxicity that occurs. Enzymes capable of bioactivating as well as detoxifying xenobiotics are expressed in the ovary and their impact on ovotoxicity has been partially characterized for trichloroethylene, 7,12-dimethylbenz[a]anthracene, and 4-vinylcyclohexene. This review will discuss those studies, as well as illustrate where knowledge gaps remain for chemicals that have also been established as ovotoxicants. -- Highlights: ► Summary of ovotoxicant action during ovotoxicity. ► Discussion of impact of biotransformation on chemical toxicity. ► Identification of knowledge gaps in chemical metabolism.

  13. Indoor air chemistry: Formation of organic acids and aldehydes

    SciTech Connect

    Zhang, J.; Lioy, P.J. ||; Wilson, W.E.

    1994-12-31

    Laying emphasis on the formation of aldehydes and organic acids, the study has examined the gas-phase reactions of ozone with unsaturated VOCs. The formation of formaldehyde and formic acid was observed for all the three selected unsaturated VOCs: styrene, limonene, and 4-vinylcyclohexene. In addition, benzaldehyde was detected in the styrene-ozone-air reaction system, and acetic acid was also found in limonene-ozone-air system. The study has also examined the gas-phase reactions among formaldehyde, ozone, and nitrogen dioxide and found the formation of formic acid. The nitrate radical was suggested to play an important role in converting formaldehyde into formic acid. Experiments for all the reactions were conducted by using a 4.3 m{sup 3} Teflon chamber. Since the conditions for the reactions were similar to those for indoor environments, the results from the study can be implicated to real indoor situations and can be employed to support the findings and suggestions from the previous studies: certain aldehydes and organic acids could be generated by indoor chemistry.

  14. Long Term Outcome after Application of the Angio-Seal Vascular Closure Device in Minipigs

    PubMed Central

    Kabelitz, Lisa; Nonn, Andrea; Nolte, Kay W.; Nikoubashman, Omid; Othman, Ahmed; Heringer, Sarah; Kramer, Martin; Wiesmann, Martin; Brockmann, Marc A.

    2016-01-01

    Minipigs are frequently used in (neuro-)interventional research. Longitudinal experiments may require repeated vessel access via the femoral artery. Anticoagulation and incompliance of the animals necessitates the use of a vascular closure device (VCD). The effects of the Angio-Seal VCD in minipigs were longitudinally assessed. Minipig (42±8.4 kg body weight) femoral arteries were sealed using the 8F (n = 6) or 6F (n = 7) Angio-Seal VCD. The pre-interventional femoral artery diameter was 5.1±0.4 mm (4.3–5.8 mm). Sealed puncture sites were analysed angiographically as well as by computed tomography angiography (CTA) for a mean period of 14.1±8.0 weeks (1–22 weeks). All animals were constantly treated with acetylsalicylic acid (ASS) (450 mg/d (n = 7) or 100 mg/d (n = 1)) and clopidogrel (75 mg/d (n = 8)). Non-instrumented (n = 2) and arteries sealed using the VCD (n = 2) were examined histologically. No postoperative hemorrhagic complications were observed. Three arteries were occluded after VCD placement (1 animal diagnosed after 4 weeks (8F), 2 animals after 1 week (6F)) and remained so until the end of the experiments after 22, 12 and 4 weeks, respectively. In one artery a 50% stenosis 8 weeks after application of a 6F Angio-Seal was detected. In 69.2% (n = 9) the VCD was applied without complications. Histopathological analysis of the sealed arterial segments showed subtotal obliteration of the vessel lumen, formation of collagenous tissue and partial damage of the internal elastic lamina. The Angio-Seal VCD prevents relevant hemorrhagic complications in minipigs treated with dual platelet inhibition, but is associated with increased vessel occlusion rates. PMID:27682594

  15. pH titration monitored by quantum cascade laser-based vibrational circular dichroism.

    PubMed

    Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen

    2014-04-10

    Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions.

  16. pH titration monitored by quantum cascade laser-based vibrational circular dichroism.

    PubMed

    Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen

    2014-04-10

    Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions. PMID:24655319

  17. Site-specific conformational determination in thermal unfolding studies of helical peptides using vibrational circular dichroism with isotopic substitution

    PubMed Central

    Silva, R. A. G. D.; Kubelka, Jan; Bour, Petr; Decatur, Sean M.; Keiderling, Timothy A.

    2000-01-01

    Understanding the detailed mechanism of protein folding requires dynamic, site-specific stereochemical information. The short time response of vibrational spectroscopies allows evaluation of the distribution of populations in rapid equilibrium as the peptide unfolds. Spectral shifts associated with isotopic labels along with local stereochemical sensitivity of vibrational circular dichroism (VCD) allow determination of the segment sequence of unfolding. For a series of alanine-rich peptides that form α-helices in aqueous solution, we used isotopic labeling and VCD to demonstrate that the α-helix noncooperatively unwinds from the ends with increasing temperature. For these blocked peptides, the C-terminal is frayed at 5°C. Ab initio level theoretical simulations of the IR and VCD band shapes are used to analyze the spectra and to confirm the conformation of the labeled components. The VCD signals associated with the labeled residues are amplified by coupling to the nonlabeled parts of the molecule. Thus small labeled segments are detectable and stereochemically defined in moderately large peptides in this report of site-specific peptide VCD conformational analysis. PMID:10880566

  18. Mensuration of cervical vertebral ratios in Doberman pinschers and Great Danes.

    PubMed

    Drost, Wm Tod; Lehenbauer, Terry W; Reeves, Jeff

    2002-01-01

    Canine cervical vertebral instability is a complex syndrome involving cervical spinal cord compressive lesions. Doberman pinschers and Great Danes are the most commonly affected breeds. Measurements of vertebral canal diameter (VCD), vertebral body height (H), and vertebral body length (L) were made from C3-C7 in 24 Doberman pinschers and 8 Great Danes by using digital and analog techniques. Significant differences between affected and unaffected sites were noted for Doberman pinschers at C6 (P = 0.039) and C7 (P = 0.027) using analog measurements of VCD/H, and Great Danes at C6 using analog (P = 0.041) and digital (P = 0.004) measurements of VCD/L. Cervical vertebral ratios have potential as a breed-specific screening tool for cervical vertebral instability and warrant longitudinal studies.

  19. Death Due to an Unusual Angio-Seal-Related Complication: Case Report and Literature Review.

    PubMed

    D'Ovidio, Cristian; Sablone, Sara; Carnevale, Aldo

    2016-09-01

    Angio-SealTM is a vascular closure device (VCD) that can be applied to the femoral artery following cardiac catheterization to achieve hemostasis. Although it has been demonstrated to be superior to conventional manual pressure and to reduce time to hemostasis and patient ambulation, the use of this VCD is not without its complications. In this report, we describe the case of a 55-year-old man who died due to an extremely rare event that occurred several hours after the deployment of an Angio-SealTM VCD: acute complete transverse laceration of the femoral artery that occurred because of the particular fragility of the vessel due to an unrecognized and asymptomatic arteriosclerotic disease. Few data are available in the literature about the incidence of such events, and much more remains to be done to determine how to prevent and manage its occurrence.

  20. An atypical presentation of visual conversion disorder.

    PubMed

    Foutch, Brian K

    2015-01-01

    Nonorganic vision loss accounts for up to 5% of patients and presents in two forms, malingering and visual conversion disorder (VCD). It is described a case of VCD in a new mother struggling both with her husband being deployed overseas and the recent death of her father. In addition, she had been evaluated for a concussion secondary to a motor vehicle accident three months prior. An inexpensive series of clinical tests were performed to rule out organic disease and obtained equivocal results. Some tests revealed intact vision in the affected eye while others supported a neurological cause for the vision loss. However, the patient quickly recovered normal visual acuity when encouraged to discuss situations that have been causing emotional stress. This almost immediate recovery of vision confirmed the diagnosis of VCD. This report should make primary eye care professionals more aware of visual conversion disorder and its clinical evaluation.

  1. (2R*,4R*,7S*,10R*,12R*)-3,11,13,15-Tetra­oxa­penta­cyclo­[5.5.3.01,7.02,4.010,12]penta­deca-5,8-dien-14-one

    PubMed Central

    Mehta, Goverdhan; Sen, Saikat; Kumar, C. S. Ananda

    2013-01-01

    The title compound, C11H8O5, features a ‘skipped’ diene, an anti-bis­(epoxide) and a cyclic carbonate, all embedded in a densely functionalized [4.4.3]propellane scaffold. The crystal packing of this diepoxide is effected primarily by C—H⋯O hydrogen bonds, which link the mol­ecules into tapes along the b axis. Inter-tape connectivity is brought about by centrosymmetrically disposed pairs of C⋯O contacts [3.183 (4) Å] between the Cδ+=Oδ- dipoles of neighbouring carbonate moieties. PMID:24098200

  2. Regioselective and Stereospecific Copper-Catalyzed Deoxygenation of Epoxides to Alkenes.

    PubMed

    Yu, Jingxun; Zhou, Yu; Lin, Zhenyang; Tong, Rongbiao

    2016-09-16

    Two copper salts (Cu(CF3CO2)2 and IMesCuCl) were identified as earth-abundant, inexpensive, but effective metal catalysts together with diazo malonate for chemo-/regioselective and stereospecific deoxygenation of various epoxides with tolerance of common functional groups (alkene, ketone, ester, p-methoxybenzyl, benzyl, tert-butyldimethylsilyl, and triisopropylsilyl). In particular, the unprecedented regioselectivity allowed for the first time monodeoxygenation of diepoxides to alkenyl epoxides. Density functional theory mechanistic studies showed that the deoxygenation occurred by collapsing the free ylide, unfavoring the possible intuitive pathway via cycloreversion of possible oxetane. PMID:27596225

  3. Differential Regulation of Disheveled in a Novel Vegetal Cortical Domain in Sea Urchin Eggs and Embryos: Implications for the Localized Activation of Canonical Wnt Signaling

    PubMed Central

    Peng, ChiehFu Jeff; Wikramanayake, Athula H.

    2013-01-01

    Pattern formation along the animal-vegetal (AV) axis in sea urchin embryos is initiated when canonical Wnt (cWnt) signaling is activated in vegetal blastomeres. The mechanisms that restrict cWnt signaling to vegetal blastomeres are not well understood, but there is increasing evidence that the egg’s vegetal cortex plays a critical role in this process by mediating localized “activation” of Disheveled (Dsh). To investigate how Dsh activity is regulated along the AV axis, sea urchin-specific Dsh antibodies were used to examine expression, subcellular localization, and post-translational modification of Dsh during development. Dsh is broadly expressed during early sea urchin development, but immunolocalization studies revealed that this protein is enriched in a punctate pattern in a novel vegetal cortical domain (VCD) in the egg. Vegetal blastomeres inherit this VCD during embryogenesis, and at the 60-cell stage Dsh puncta are seen in all cells that display nuclear β-catenin. Analysis of Dsh post-translational modification using two-dimensional Western blot analysis revealed that compared to Dsh pools in the bulk cytoplasm, this protein is differentially modified in the VCD and in the 16-cell stage micromeres that partially inherit this domain. Dsh localization to the VCD is not directly affected by disruption of microfilaments and microtubules, but unexpectedly, microfilament disruption led to degradation of all the Dsh pools in unfertilized eggs over a period of incubation suggesting that microfilament integrity is required for maintaining Dsh stability. These results demonstrate that a pool of differentially modified Dsh in the VCD is selectively inherited by the vegetal blastomeres that activate cWnt signaling in early embryos, and suggests that this domain functions as a scaffold for localized Dsh activation. Localized cWnt activation regulates AV axis patterning in many metazoan embryos. Hence, it is possible that the VCD is an evolutionarily conserved

  4. Infrared, vibrational circular dichroism, and Raman spectral simulations for β-sheet structures with various isotopic labels, interstrand, and stacking arrangements using density functional theory.

    PubMed

    Welch, William R W; Kubelka, Jan; Keiderling, Timothy A

    2013-09-12

    Infrared (IR), Raman, and vibrational circular dichroism (VCD) spectral variations for different β-sheet structures were studied using simulations based on density functional theory (DFT) force field and intensity computations. The DFT vibrational parameters were obtained for β-sheet fragments containing nine-amides and constrained to a variety of conformations and strand arrangements. These were subsequently transferred onto corresponding larger β-sheet models, normally consisting of five strands with ten amides each, for spectral simulations. Further extension to fibril models composed of multiple stacked β-sheets was achieved by combining the transfer of DFT parameters for each sheet with dipole coupling methods for interactions between sheets. IR spectra of the amide I show different splitting patterns for parallel and antiparallel β-sheets, and their VCD, in the absence of intersheet stacking, have distinct sign variations. Isotopic labeling by (13)C of selected residues yields spectral shifts and intensity changes uniquely sensitive to relative alignment of strands (registry) for antiparallel sheets. Stacking of multiple planar sheets maintains the qualitative spectral character of the single sheet but evidences some reduction in the exciton splitting of the amide I mode. Rotating sheets with respect to each other leads to a significant VCD enhancement, whose sign pattern and intensity is dependent on the handedness and degree of rotation. For twisted β-sheets, a significant VCD enhancement is computed even for sheets stacked with either the same or opposite alignments and the inter-sheet rotation, depending on the sense, can either further increase or weaken the enhanced VCD intensity. In twisted, stacked structures (without rotation), similar VCD amide I patterns (positive couplets) are predicted for both parallel and antiparallel sheets, but different IR intensity distributions still enable their differentiation. Our simulation results prove useful

  5. The Clusters-in-a-Liquid Approach for Solvation: New Insights from the Conformer Specific Gas Phase Spectroscopy and Vibrational Optical Activity Spectroscopy

    PubMed Central

    Perera, Angelo S.; Thomas, Javix; Poopari, Mohammad R.; Xu, Yunjie

    2016-01-01

    Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as powerful spectroscopic tools for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have been explored. In this review article, we first select a few examples to demonstrate the unique sensitivity of VCD spectral signatures to both bulk solvent effects and explicit hydrogen-bonding interactions in solution. Second, we discuss the induced solvent chirality, or chiral transfer, VCD spectral features observed in the water bending band region in detail. From these chirality transfer spectral data, the related conformer specific gas phase spectroscopic studies of small chiral hydration clusters, and the associated matrix isolation VCD experiments of hydrogen-bonded complexes in cold rare gas matrices, a general picture of solvation in aqueous solution emerges. In such an aqueous solution, some small chiral hydration clusters, rather than the chiral solutes themselves, are the dominant species and are the ones that contribute mainly to the experimentally observed VCD features. We then review a series of VCD studies of amino acids and their derivatives in aqueous solution under different pHs to emphasize the importance of the inclusion of the bulk solvent effects. These experimental data and the associated theoretical analyses are the foundation for the proposed “clusters-in-a-liquid” approach to account for solvent effects effectively. We present several approaches to identify and build such representative chiral hydration clusters. Recent studies which applied molecular dynamics simulations and the subsequent snapshot averaging approach to generate the ROA, VCD, electronic CD, and optical rotatory dispersion spectra are also reviewed. Challenges associated with

  6. Waste water processing technology for Space Station Freedom - Comparative test data analysis

    NASA Technical Reports Server (NTRS)

    Miernik, Janie H.; Shah, Burt H.; Mcgriff, Cindy F.

    1991-01-01

    Comparative tests were conducted to choose the optimum technology for waste water processing on SSF. A thermoelectric integrated membrane evaporation (TIMES) subsystem and a vapor compression distillation subsystem (VCD) were built and tested to compare urine processing capability. Water quality, performance, and specific energy were compared for conceptual designs intended to function as part of the water recovery and management system of SSF. The VCD is considered the most mature and efficient technology and was selected to replace the TIMES as the baseline urine processor for SSF.

  7. Preliminary Design Program: Vapor Compression Distillation Flight Experiment Program

    NASA Technical Reports Server (NTRS)

    Schubert, F. H.; Boyda, R. B.

    1995-01-01

    This document provides a description of the results of a program to prepare a preliminary design of a flight experiment to demonstrate the function of a Vapor Compression Distillation (VCD) Wastewater Processor (WWP) in microgravity. This report describes the test sequence to be performed and the hardware, control/monitor instrumentation and software designs prepared to perform the defined tests. the purpose of the flight experiment is to significantly reduce the technical and programmatic risks associated with implementing a VCD-based WWP on board the International Space Station Alpha.

  8. Vapor Compression Distillation Flight Experiment

    NASA Technical Reports Server (NTRS)

    Hutchens, Cindy F.

    2002-01-01

    One of the major requirements associated with operating the International Space Station is the transportation -- space shuttle and Russian Progress spacecraft launches - necessary to re-supply station crews with food and water. The Vapor Compression Distillation (VCD) Flight Experiment, managed by NASA's Marshall Space Flight Center in Huntsville, Ala., is a full-scale demonstration of technology being developed to recycle crewmember urine and wastewater aboard the International Space Station and thereby reduce the amount of water that must be re-supplied. Based on results of the VCD Flight Experiment, an operational urine processor will be installed in Node 3 of the space station in 2005.

  9. The potential of sec-butylpropylacetamide (SPD) and valnoctamide and their individual stereoisomers in status epilepticus.

    PubMed

    Shekh-Ahmad, Tawfeeq; Mawasi, Hafiz; McDonough, John H; Yagen, Boris; Bialer, Meir

    2015-08-01

    sec-Butylpropylacetamide (SPD) is a one-carbon homologue of valnoctamide (VCD), a chiral constitutional isomer of valproic acid's (VPA) corresponding amide--valpromide. Racemic-SPD and racemic-VCD possess a unique and broad-spectrum antiseizure profile superior to that of VPA. In addition, SPD blocks behavioral and electrographic status epilepticus (SE) induced by pilocarpine and the organophosphates soman and paraoxon. Valnoctamide has similar activity as SPD in the soman-induced SE model. The activity of SPD and VCD against SE is superior to that of diazepam and midazolam in terms of rapid onset, potency, and ability to block SE when given 20 to 60 min after seizure onset. sec-Butylpropylacetamide and VCD possess two stereogenic carbons in their chemical structure and, thus, exist as a racemic mixture of four individual stereoisomers. The anticonvulsant activity of the individual stereoisomers of SPD and VCD was comparatively evaluated in several anticonvulsant rodent models including the benzodiazepine-resistant SE model. sec-Butylpropylacetamide has stereoselective pharmacokinetics (PK) and pharmacodynamics (PD). The higher clearance of (2R,3S)-SPD and (2S,3R)-SPD led to a 50% lower plasma exposure and, consequently, to a lower anticonvulsant activity compared to racemic-SPD and its two other stereoisomers. Racemic-SPD, (2S,3S)-SPD, and (2R,3R)-SPD have similar anticonvulsant activities and PK profiles that are better than those of (2R,3S)-SPD and (2S,3R)-SPD. Valnoctamide has a stereoselective PK with (2S,3S)-VCD exhibiting the lowest clearance and, consequently, a twice-higher plasma exposure than all other stereoisomers. Nevertheless, there was less stereoselectivity in VCD anticonvulsant activity, and each stereoisomer had similar ED50 values in most models. sec-Butylpropylacetamide and VCD stereoisomers did not cause teratogenicity (i.e., neural tube defect) in mice at doses 3-12 times higher than their anticonvulsant-ED50 values. This article is part of a

  10. The effects of self-aggregation on the vibrational circular dichroism and optical rotation measurements of glycidol.

    PubMed

    Yang, Guochun; Xu, Yunjie

    2008-12-01

    The noncovalent interactions between glycidol molecules in the CDCl3 solvent have been studied by means of vibrational absorption (VA), vibrational circular dichroism (VCD), optical rotation (OR) spectroscopy and density functional theory (DFT) calculations. The concentration dependence of the VA and VCD spectra and OR measurements at five excitation wavelengths, i.e. 589, 578, 546, 436 and 365 nm, has been reported. To model the effects of self-aggregation of glycidol on the measurements, the energetic and conformational properties of the glycidol monomer, dimer and trimer were evaluated and the corresponding VA, VCD and OR spectra were simulated. The results show that at 0.2 M or lower concentrations the self-aggregation of glycidol is negligible since the simulated VA and VCD spectra, with the contribution from only the monomeric glycidol conformers, reproduce well the features in the experimental spectra. At 3.5 M, the binary conformers dominate, while at the intermediate concentration of 1.1 M, both the monomeric and binary conformers are important. The comparison of the experimental and theoretical OR values supports the above conclusions. This work shows the potential of using multiple chiroptical spectroscopic methods in combination with theoretical calculations to probe the self-aggregation process of chiral molecules in solution. Such studies can in turn help to achieve reliably absolute configuration determinations in the cases when chiral molecules self-aggregate profusely.

  11. Application of dielectric spectroscopy for monitoring high cell density in monoclonal antibody producing CHO cell cultivations.

    PubMed

    Párta, László; Zalai, Dénes; Borbély, Sándor; Putics, Akos

    2014-02-01

    The application of dielectric spectroscopy was frequently investigated as an on-line cell culture monitoring tool; however, it still requires supportive data and experience in order to become a robust technique. In this study, dielectric spectroscopy was used to predict viable cell density (VCD) at industrially relevant high levels in concentrated fed-batch culture of Chinese hamster ovary cells producing a monoclonal antibody for pharmaceutical purposes. For on-line dielectric spectroscopy measurements, capacitance was scanned within a wide range of frequency values (100-19,490 kHz) in six parallel cell cultivation batches. Prior to detailed mathematical analysis of the collected data, principal component analysis (PCA) was applied to compare dielectric behavior of the cultivations. PCA analysis resulted in detecting measurement disturbances. By using the measured spectroscopic data, partial least squares regression (PLS), Cole-Cole, and linear modeling were applied and compared in order to predict VCD. The Cole-Cole and the PLS model provided reliable prediction over the entire cultivation including both the early and decline phases of cell growth, while the linear model failed to estimate VCD in the later, declining cultivation phase. In regards to the measurement error sensitivity, remarkable differences were shown among PLS, Cole-Cole, and linear modeling. VCD prediction accuracy could be improved in the runs with measurement disturbances by first derivative pre-treatment in PLS and by parameter optimization of the Cole-Cole modeling.

  12. The Use of ExoSeal Vascular Closure Device for Direct Antegrade Superficial Femoral Artery Puncture Site Hemostasis

    SciTech Connect

    Rimon, Uri Khaitovich, Boris; Yakubovich, Dmitry; Bensaid, Paul Golan, Gil; Silverberg, Daniel

    2015-06-15

    PurposeThis study was designed to assess the efficacy and safety of the ExoSeal vascular closure device (VCD) to achieve hemostasis in antegrade access of the superficial femoral artery (SFA).MethodsWe retrospectively reviewed the outcome of ExoSeal VCD used for hemostasis in 110 accesses to the SFA in 93 patients between July 2011 and July 2013. All patients had patent proximal SFA based on computer tomography angiography or ultrasound duplex. Arterial calcifications at puncture site were graded using fluoroscopy. The SFA was accessed in an antegrade fashion with ultrasound or fluoroscopic guidance. In all patients, 5–7F vascular sheaths were used. The ExoSeal VCD was applied to achieve hemostasis at the end of the procedure. All patients were clinically examined and had ultrasound duplex exam for any puncture site complications during the 24 h postprocedure.ResultsIn all procedures, the ExoSeal was applied successfully. We did not encounter any device-related technical failure. There were four major complications in four patients (3.6 %): three pseudoaneurysms, which were treated with direct thrombin injection, and one hematoma, which necessitated transfusion of two blood units. All patients with complications were treated with anticoagulation preprocedure or received thrombolytic therapy.ConclusionsThe ExoSeal VCD can be safely used for antegrade puncture of the SFA, with a high procedural success rate (100 %) and a low rate of access site complications (3.6 %)

  13. Discrimination of Axial and Central Stereogenic Elements in Chiral Bis(oxazolines) Based on Atropisomeric 3,3'-Bithiophene Scaffolds Through Chiroptical Spectroscopies.

    PubMed

    Gabrieli, Sara; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Benincori, Tiziana

    2016-10-01

    Two diastereoisomeric pairs of bis-oxazolines, provided with a stereogenic center at carbon 4 and based on the 3,3'-bithiophene atropisomeric scaffold, were synthesized and structurally characterized. They differ in the substituents at positions 2 and 5 of the thiophene rings, which are functionalized with methyl (1) or phenyl (2) groups, respectively. In vibrational circular dichroism (VCD) spectra, recorded in CCl4 solutions, it is possible to distinctly recognize the characteristic features of axial and central stereogenic elements. In tandem with Density Functional Theory (DFT) calculations, the absolute configuration (AC) of the diastereoisomers was safely established. In this case, VCD was shown to be superior to ECD (electronic circular dichroism) in the assignment of AC. The normal modes, evaluated from DFT calculations, show that the VCD signals in correspondence with the stereogenic axis of the bithiophene unit are different for 1 and 2. The VCD spectra of a molecular analog of 1, the (S)-2,2',5,5'-tetramethyl-4,4'-bis-(diphenylphosphino)-3,3'-bithiophene oxide (3), characterized by the same 3,3'-bithiophene scaffold, but devoid of stereogenic centers, exhibits signals similar to those observed in the case of diastereoisomer (aS,R,R)-1a, associated with almost identical normal modes. Chirality 28:686-695, 2016. © 2016 Wiley Periodicals, Inc. PMID:27670248

  14. Importance of Solvation in Understanding the Chiroptical Spectra of Natural Products in Solution Phase: Garcinia Acid Dimethyl Ester

    PubMed Central

    Polavarapu, Prasad L.; Scalmani, Giovanni; Hawkins, Edward K.; Rizzo, Carmelo; Jeirath, Neha; Ibnusaud, Ibrahim; Habel, Deenamma; Nair, Divya Sadasivan; Haleema, Simimole

    2013-01-01

    The optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectra of (+)-garcinia acid dimethyl ester have been measured and analyzed by comparison with the corresponding spectra predicted by quantum chemical methods for (2S,3S)-garcinia acid dimethyl ester. For solution-phase calculations the recently developed continuous surface charge polarizable continuum model (PCM) has been used. It is found that gas-phase predictions and PCM predictions at the B3LYP/aug-cc-pVDZ level yield nearly mirror-image ECD spectra in the 190–250 nm region for the same absolute configuration and that gas-phase ECD predictions lead to incorrect absolute configuration. At the CAM-B3LYP/aug-cc-pVDZ level, however, gas-phase predictions and PCM predictions of ECD in the 190–250 nm region are not so different, but PCM predictions provide better agreement with the experimental observations. For carbonyl stretching vibrations, the vibrational band positions predicted at the B3LYP/aug-cc-pVDZ level in gas-phase calculations differ significantly from the corresponding experimentally observed band positions, and this discrepancy has also been corrected by the use of PCM. In addition, the solution-phase VCD predictions provided better agreement (with experimental VCD observations) than gas-phase VCD predictions. These observations underscore the importance of including solvent effects in quantum chemical calculations of chiroptical spectroscopic properties. PMID:21114277

  15. Importance of solvation in understanding the chiroptical spectra of natural products in solution phase: garcinia acid dimethyl ester.

    PubMed

    Polavarapu, Prasad L; Scalmani, Giovanni; Hawkins, Edward K; Rizzo, Carmelo; Jeirath, Neha; Ibnusaud, Ibrahim; Habel, Deenamma; Nair, Divya Sadasivan; Haleema, Simimole

    2011-03-25

    The optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectra of (+)-garcinia acid dimethyl ester have been measured and analyzed by comparison with the corresponding spectra predicted by quantum chemical methods for (2S,3S)-garcinia acid dimethyl ester. For solution-phase calculations the recently developed continuous surface charge polarizable continuum model (PCM) has been used. It is found that gas-phase predictions and PCM predictions at the B3LYP/aug-cc-pVDZ level yield nearly mirror-image ECD spectra in the 190-250 nm region for the same absolute configuration and that gas-phase ECD predictions lead to incorrect absolute configuration. At the CAM-B3LYP/aug-cc-pVDZ level, however, gas-phase predictions and PCM predictions of ECD in the 190-250 nm region are not so different, but PCM predictions provide better agreement with the experimental observations. For carbonyl stretching vibrations, the vibrational band positions predicted at the B3LYP/aug-cc-pVDZ level in gas-phase calculations differ significantly from the corresponding experimentally observed band positions, and this discrepancy has also been corrected by the use of PCM. In addition, the solution-phase VCD predictions provided better agreement (with experimental VCD observations) than gas-phase VCD predictions. These observations underscore the importance of including solvent effects in quantum chemical calculations of chiroptical spectroscopic properties. PMID:21114277

  16. Spiro Fused Diterpene-Indole Alkaloids from a Creek-Bottom-Derived Aspergillus terreus

    PubMed Central

    Cai, Shengxin; Du, Lin; Gerea, Alexandra L.; King, Jarrod B.; You, Jianlan

    2013-01-01

    Four metabolites, teraspiridoles A–D (2–5), formed from the merger of diterpene and modified indole scaffold were obtained from an Aspergillus terreus isolate. The structures and absolute configurations of these natural products were established using NMR, mass spectrometry, Marfey’s method, VCD, and ECD data. Teraspiridole B (3) exhibited weak inhibition of planaria regeneration/survival. PMID:23924243

  17. Mechanism of actin filament nucleation by the bacterial effector VopL

    SciTech Connect

    Yu, Bingke; Cheng, Hui-Chun; Brautigam, Chad A.; Tomchick, Diana R.; Rosen, Michael K.

    2012-05-02

    Vibrio parahaemolyticus protein L (VopL) is an actin nucleation factor that induces stress fibers when injected into eukaryotic host cells. VopL contains three N-terminal Wiskott-Aldrich homology 2 (WH2) motifs and a unique VopL C-terminal domain (VCD). We describe crystallographic and biochemical analyses of filament nucleation by VopL. The WH2 element of VopL does not nucleate on its own and requires the VCD for activity. The VCD forms a U-shaped dimer in the crystal, stabilized by a terminal coiled coil. Dimerization of the WH2 motifs contributes strongly to nucleation activity, as do contacts of the VCD to actin. Our data lead to a model in which VopL stabilizes primarily lateral (short-pitch) contacts between actin monomers to create the base of a two-stranded filament. Stabilization of lateral contacts may be a common feature of actin filament nucleation by WH2-based factors.

  18. Post-Thaw Viable CD45+ Cells and Clonogenic Efficiency are Associated with Better Engraftment and Outcomes after Single Cord Blood Transplantation in Adult Patients with Malignant Diseases.

    PubMed

    Castillo, Nerea; García-Cadenas, Irene; Barba, Pere; Martino, Rodrigo; Azqueta, Carmen; Ferrà, Christelle; Canals, Carme; Sierra, Jorge; Valcárcel, David; Querol, Sergio

    2015-12-01

    The quantity of cells is widely accepted as the main factor influencing the outcome after umbilical cord blood transplantation (UCBT) however, the quality of the cord blood units (CBUs) has been less studied. In order to determine the impact of qualitative variables in UCBT outcomes, we conducted a multicenter retrospective study in adult patients with hematological malignancies who underwent single UCBT after a common myeloablative conditioning regimen. One hundred and ten patients from 3 institutions [median age, 35 years (range 18-55)] were included. Quantitative (TNC and total CD34+cells) and qualitative variables [viable CD45+ (vCD45+), vCD34+ and clonogenic efficiency [(CLONE), quotient of post-thaw colony-forming units (CFU)] and pre-freeze CD34+ cells predicted engraftment in univariate analysis however, only 2 qualitative variables remained significant in the multivariate analysis. Infusion of more than 2 × 10(7) post-thaw vCD45+ cells per kilogram was significantly associated with faster neutrophil (P = .01), platelet engraftment (P = .01), higher disease-free (P = .01) and overall survival (0.02). In addition, CLONE ≥ 20% predicted a faster neutrophil (P = .005), platelet engraftment (P = .01) and contributed to decrease the non-relapse mortality (P = .02). Our study suggests that the vCD45+ cells dose and CLONE are powerful surrogate markers of graft quality and can potentially help on CBUs selection if tested with representative reference samples.

  19. Explicit Consideration of Water Molecules to Study Vibrational Circular DICHROÎSM of Monosaccharide's

    NASA Astrophysics Data System (ADS)

    Moussi, Sofiane; Ouamerali, Ourida

    2014-06-01

    Carbohydrates have multiples roles in biological systems. It has been found that the glycoside bond is fundamentally important in many aspects of chemistry and biology and forms the basis of carbohydrate chemistry. That means the stereochemical information, namely, glycosidic linkages α or β, gives an significant features of the carbohydrate glycosidation position of the glycosylic acceptor. For these reasons, much effort was made for the synthesis and analysis of the glycoside bond. Vibrational circular dichroism VCD has some advantages over conventional electronic circular dichroism (ECD) due to the applicability to all organic molecules and the reliability of ab initio quantum calculation. However, for a molecule with many chiral centers such as carbohydrates, determination of the absolute configuration tends to be difficult because the information from each stereochemical center is mixed and averaged over the spectrum. In the CH stretching region, only two VCD studies on carbohydrates have been reported and spectra--structure correlation, as determined for the glycoside band, remains to be investigated. T. Taniguchi and collaborators report that methyl glycosides exhibit a characteristic VCD peak, the sign of which solely reflects the C-1 absolute configuration. This work is a theoretical contribution to study the behaviour of VCD spectrum's of the monosaccharides when the water molecules are taken explicitly. This study is focused on six different monosaccharides in theirs absolute configuration R and S. We used the method of density functional theory DFT by means of the B3LYP hybrid functional and 6-31G * basis set.

  20. Using Student Video Cases to Assess Pre-service Elementary Teachers' Engineering Teaching Responsiveness

    NASA Astrophysics Data System (ADS)

    Dalvi, Tejaswini; Wendell, Kristen

    2016-10-01

    Our study addresses the need for new approaches to prepare novice elementary teachers to teach both science and engineering, and for new tools to measure how well those approaches are working. This in particular would inform the teacher educators of the extent to which novice teachers are developing expertise in facilitating their students' engineering design work. One important dimension to measure is novice teachers' abilities to notice the substance of student thinking and to respond in productive ways. This teacher noticing is particularly important in science and engineering education, where students' initial, idiosyncratic ideas and practices influence the likelihood that particular instructional strategies will help them learn. This paper describes evidence of validity and reliability for the Video Case Diagnosis (VCD) task, a new instrument for measuring pre-service elementary teachers' engineering teaching responsiveness. To complete the VCD, participants view a 6-min video episode of children solving an engineering design problem, describe in writing what they notice about the students' science ideas and engineering practices, and propose how a teacher could productively respond to the students. The rubric for scoring VCD responses allowed two independent scorers to achieve inter-rater reliability. Content analysis of the video episode, systematic review of literature on science and engineering practices, and solicitation of external expert educator responses establish content validity for VCD. Field test results with three different participant groups who have different levels of engineering education experience offer evidence of construct validity.

  1. On the handedness of helical aggregates of C3 tricarboxamides: a multichiroptical characterization.

    PubMed

    Nieto-Ortega, Belén; García, Fátima; Longhi, Giovanna; Castiglioni, Ettore; Calbo, Joaquín; Abbate, Sergio; López Navarrete, Juan T; Ramírez, Francisco J; Ortí, Enrique; Sánchez, Luis; Casado, Juan

    2015-06-18

    A complete chiroptical characterization of the supramolecular polymers formed by tricarboxamides and is performed using ECD, VCD and CPL dichroic techniques. The helical aggregates show an intense CPL signal and their absolute P- or M-configuration is assigned with the help of theoretical calculations. PMID:25960027

  2. A Study of External Galaxies Detected by the {ital COBE} Diffuse Infrared Background Experiment

    SciTech Connect

    Odenwald, S.; Newmark, J.; Smoot, G.

    1998-06-01

    A comparison of the {ital COBE} Diffuse Infrared Background Experiment (DIRBE) all-sky survey with the locations of known galaxies in the {ital IRAS} Catalog of Extragalactic Objects and the Center for Astrophysics Catalog of Galaxies led to the detection of as many as 57 galaxies. In this paper, we present the photometric data for these galaxies and an analysis of the seven galaxies that were detected at {lambda} {gt} 100 {mu}m. Estimates of the ratio of the mass of the cold dust (CD) component detected at {ital T}{sub {ital d}} = 20{endash}30 K to a very cold dust (VCD) component with {ital T}{sub {ital d}} {approx} 10{endash}15 K suggest that between 2{percent}{endash}100{percent} of the cirrus-like CD mass can also exist in many of these galaxies as VCD. In one galaxy, M33, the DIRBE photometry at 240 {mu}m suggests as much as 26 times as much VCD may be present as compared to the cirrus-like component. Further submillimeter measurements of this galaxy are required to verify such a large population of VCD. We also present 10 galaxies that were detected in the sky region not previously surveyed by {ital IRAS} and that can be used to construct a flux-limited all-sky catalog of galaxies brighter than 1000 Jy with a modest completeness limit of about 65{percent}. {copyright} {ital {copyright} 1998.} {ital The American Astronomical Society}

  3. Diagnostic criteria for vascular cognitive disorders: a VASCOG statement

    PubMed Central

    Sachdev, Perminder; Kalaria, Raj; O’Brien, John; Skoog, Ingmar; Alladi, Suvarna; Black, Sandra E; Blacker, Deborah; Blazer, Dan; Chen, Christopher; Chui, Helena; Ganguli, Mary; Jellinger, Kurt; Jeste, Dilip V.; Pasquier, Florence; Paulsen, Jane; Prins, Niels; Rockwood, Kenneth; Roman, Gustavo; Scheltens, Philip

    2014-01-01

    Background Several sets of diagnostic criteria have been published for vascular dementia (VaD) since the 1960s. The continuing ambiguity in VaD definition warrants a critical re-examination. Methods Participants at a special symposium of the International Society for Vascular Behavioral and Cognitive Disorders (VASCOG) in 2009 critiqued the current criteria. They drafted a proposal for a new set of criteria, later reviewed through multiple drafts by the group, including additional experts and the members of the Neurocognitive Disorders Work Group of the DSM-5 Task Force. Results Cognitive disorders of vascular etiology are a heterogeneous group of disorders with diverse pathologies and clinical manifestations, discussed broadly under the rubric of vascular cognitive disorders (VCD). The continuum of vascular cognitive impairment is recognized by the categories of Mild Vascular Cognitive Disorder, and Vascular Dementia or Major Vascular Cognitive Disorder. Diagnostic thresholds are defined. Clinical and neuroimaging criteria are proposed for establishing vascular etiology. Subtypes of VCD are described, and the frequent co-occurrence of Alzheimer’s disease pathology emphasized. Conclusions The proposed criteria for VCD provide a coherent approach to the diagnosis of this diverse group of disorders, with a view to stimulating clinical and pathological validation studies. These criteria can be harmonized with the DSM-5 criteria such that an international consensus on the criteria for VCD may be achieved. PMID:24632990

  4. Pharmacodynamic and pharmacokinetic analysis of CNS-active constitutional isomers of valnoctamide and sec-butylpropylacetamide--Amide derivatives of valproic acid.

    PubMed

    Mawasi, Hafiz; Shekh-Ahmad, Tawfeeq; Finnell, Richard H; Wlodarczyk, Bogdan J; Bialer, Meir

    2015-05-01

    Valnoctamide (VCD) and sec-butylpropylacetamide (SPD) are CNS-active closely related amide derivatives of valproic acid with unique anticonvulsant activity. This study evaluated how small chemical changes affect the pharmacodynamics (PD; anticonvulsant activity and teratogenicity) and pharmacokinetics (PK) of three constitutional isomers of SPD [sec-butylisopropylacetamide (SID) and tert-butylisopropylacetamide (TID)] and of VCD [tert-butylethylacetamide (TED)]. The anticonvulsant activity of SID, TID, and TED was comparatively evaluated in several rodent anticonvulsant models. The PK-PD relationship of SID, TID, and TED was evaluated in rats, and their teratogenicity was evaluated in a mouse strain highly susceptible to teratogen-induced neural tube defects (NTDs). sec-Butylisopropylacetamide and TID have a similar PK profile to SPD which may contribute to their similar anticonvulsant activity. tert-Butylethylacetamide had a better PK profile than VCD (and SPD); however, this did not lead to a superior anticonvulsant activity. sec-Butylisopropylacetamide and TED did not cause NTDs at doses 4-7 times higher than their anticonvulsant ED50 values. In rats, SID, TID (ip), and TED exhibited a broad spectrum of anticonvulsant activity. However, combined anticonvulsant analysis in mice and rats shows SID as the most potent compound with similar activity to that of SPD, demonstrating that substitution of the isobutyl moiety in the SPD or VCD molecule by tert-butyl as well as a propyl-to-isopropyl replacement in the SPD molecule did not majorly affect the anticonvulsant activity.

  5. Vibrational and electronic optical activity of the chiral disulphide group: implications for disulphide bridge conformation.

    PubMed

    Bednárová, Lucie; Bour, Petr; Malon, Petr

    2010-05-15

    Using dihydrogendisulphide (H(2)S(2)), dimethyl- ((CH(3))(2)S(2)), and diethyldisulphide ((CH(3)CH(2))(2)S(2))as model molecules, theoretical ECD, VCD, and ROA spectra of nonplanar disulphides were calculated by DFT methods. Most of the calculated electronic and vibrational chiroptical features suffer an equivocal relation between calculatedsigns of ECD, VCD, or ROA and the sense of disulphide nonplanarity as noted earlier for low-lying ECD bands. This is a consequence of local C(2) symmetry of a disulphide group causing most electronic and vibrational transitions to occur as pairs falling to alternative A, B symmetry species, which become degenerate and switch their succession (and consequently the observed chiroptical sign pattern) at the energetically most favorable perpendicular conformation. According to present calculations, the key to resolving this ambiguity may involve the S-S stretching vibrational mode at approximately 500 cm(-1). The relation of signs of the relevant VCD and ROA features to sense of disulphide chirality seems simpler and less ambiguous. The right-handed arrangement of the S-S group (0 < chi(S-S) < 180 degrees) results in mostly negative VCD signals. Although relation to ROA still suffers some ambiguity, it gets clearer along the series H(2)S(2)-(CH(3))(2)S(2)-(CH(3)CH(2))(2)S(2). ROA is also attractive for the analysis of disulphide-containing peptides and proteins, because applying it to aqueous solutions is not problematic.

  6. The clusters-in-a-liquid approach for solvation: New insights from the conformer specific gas phase spectroscopy and vibrational optical activity spectroscopy

    NASA Astrophysics Data System (ADS)

    Xu, Yunjie; Perera, Angelo; Thomas, Javix; Poopari, Mohammad

    2016-02-01

    Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as a powerful spectroscopic tool for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have been explored. In this review article, we first select a few examples to demonstrate the unique sensitivity of VCD spectral signatures to both bulk solvent effects and explicit hydrogen-bonding interactions in solution. Second, we discuss the induced solvent chirality, or chiral transfer, VCD spectral features observed at the water bending band region in detail. From these chirality transfer spectral data, the related conformer specific gas phase spectroscopic studies of small chiral hydration clusters, and the associated matrix isolation VCD experiments of hydrogen-bonded complexes in cold rare gas matrices, a general picture of solvation in aqueous solution emerges. In such an aqueous solution, some small chiral hydration clusters, rather than the chiral solutes themselves, are the dominant species and are the ones who contribute mainly to the experimentally observed VCD features. We then review a series of VCD studies of amino acids and their derivatives in aqueous solution under different pHs to emphasize the importance of the inclusion of the bulk solvent effects. These experimental data and the associated theoretical analyses are the foundation for the proposed “clusters-in-a-liquid” approach to account for solvent effects effectively. We present several approaches to identify and build such representative chiral hydration clusters. Recent studies which applied molecular dynamics simulations and the subsequent snapshot averaging approach to generate the ROA, electronic CD, and optical rotatory dispersion spectra are also reviewed. Challenges associated with the

  7. Mobile MAX-DOAS observation of NO2 and comparison with OMI satellite data in the western coastal areas of the Korean peninsula.

    PubMed

    Chong, Jihyo; Kim, Young J; Gu, Myojeong; Wagner, Thomas; Song, Chul H

    2016-01-01

    Ground-based MAX-DOAS measurements have been used to retrieve column densities of atmospheric absorbers such as NO2, SO2, HCHO, and O3. In this study, mobile MAX-DOAS measurements were conducted to map the 2-D distributions of atmospheric NO2 in the western coastal areas of the Korean peninsula. A Mini-MAX-DOAS instrument was mounted on the rooftop of a mobile lab vehicle with a telescope mounted parallel to the driving direction, pointing forward. The measurements were conducted from 21 to 24 December 2010 along the western coastal areas from Gomso harbor (35.59N, 126.61E) to Gunsan harbor (35.98N, 126.67E). During mobile MAX-DOAS observations, high elevation angles were used to avoid shades from nearby obstacles. For the determination of the tropospheric vertical column density (VCD), the air mass factor (AMF) was retrieved by the so-called geometric approximation. The NO2 VCDs from 20 and 45 degree elevation angles were retrieved from mobile MAX-DOAS measurements. The tropospheric NO2 VCDs derived from mobile MAX-DOAS measurements were compared directly to those retrieved by the OMI satellite observations. Mobile MAX-DOAS VCD was in good agreement with OMI tropospheric VCD on most days. However, OMI tropospheric VCD was much higher than that of mobile MAX-DOAS on 23 December 2010. One probable reason for this difference is that OMI retrieval might overestimate NO2 VCD under haze conditions, when a pollution plume was transported over the measurement site. The mobile MAX-DOAS observations reveal much finer spatial patterns of NO2 distributions, which can provide useful information for the validation of satellite observation of atmospheric trace gases.

  8. Quantifying and Reducing Uncertainties in Estimating OMI Tropospheric Column NO2 Trend over The United States

    NASA Astrophysics Data System (ADS)

    Smeltzer, C. D.; Wang, Y.; Boersma, F.; Celarier, E. A.; Bucsela, E. J.

    2013-12-01

    We investigate the effects of retrieval radiation schemes and parameters on trend analysis using tropospheric nitrogen dioxide (NO2) vertical column density (VCD) measurements over the United States. Ozone Monitoring Instrument (OMI) observations from 2005 through 2012 are used in this analysis. We investigated two radiation schemes, provided by National Aeronautics and Space Administration (NASA TOMRAD) and Koninklijk Nederlands Meteorologisch Instituut (KNMI DAK). In addition, we analyzed trend dependence on radiation parameters, including surface albedo and viewing geometry. The cross-track mean VCD average difference is 10-15% between the two radiation schemes in 2005. As the OMI anomaly developed and progressively worsens, the difference between the two schemes becomes larger. Furthermore, applying surface albedo measurements from the Moderate Resolution Imaging Spectroradiometer (MODIS) leads to increases of estimated NO2 VCD trends over high-emission regions. We find that the uncertainties of OMI-derived NO2 VCD trends can be reduced by up to a factor of 3 by selecting OMI cross-track rows on the basis of their performance over the ocean [see abstract figure]. Comparison of OMI tropospheric VCD trends to those estimated based on the EPA surface NO2 observations indicate using MODIS surface albedo data and a more narrow selection of OMI cross-track rows greatly improves the agreement of estimated trends between satellite and surface data. This figure shows the reduction of uncertainty in OMI NO2 trend by selecting OMI cross-track rows based on the performance over the ocean. With this technique, uncertainties within the seasonal trend may be reduced by a factor of 3 or more (blue) compared with only removing the anomalous rows: considering OMI cross-track rows 4-24 (red).

  9. Organic amendment based on vermicompost and compost: differences on soil properties and maize yield.

    PubMed

    Tejada, Manuel; Benítez, Concepción

    2011-11-01

    The objective of the present study was to study the effect of two vermicomposts [animal (VCD) and vegetal origin (VGF)] and a cotton gin compost (C) at rates of 1780 and 3560 kg fresh organic matter ha(-1) for 3 years on an Typic Xerofluvent located near Seville (Spain) on soil biological properties, nutrition (leaf N, P and K concentration, pigments and soluble carbohydrate concentrations) and yield parameters of maize (Zea mays cv. Tundra) crop. All organic waste materials had a positive effect on the soil biological properties, plant nutrition and crop yield parameters, although at the end of the experimental period and at the high organic matter rate, the soil microbial biomass and dehydrogenase, urease, β-glucosidase, phosphatase and arylsulfatase activities increased more significantly in the VCD-amended soils (86.4, 85.8, 94.5, 99.3, 70.1 and 63.8%, respectively) respect to the control soil, followed by VGF-amended soils (84.8, 80.6, 92.7, 99.1, 68.3 and 61.6%, respectively) and CC-amended soils (80.5, 75.9, 89.7, 99, 65.7 and 59.9%, respectively). Leaf N, P and K contents and pigments and soluble carbohydrate contents were highest in VCD-amended soils, followed by VGF and CC treatments. Compared with the control soil, the application of VCD in soils at high doses increased the crop yield parameters, followed by VGF and CC treatments. This may have been due to a greater labile fraction of organic matter in the VCD than the VGF and CC, respectively.

  10. [Retrieval of NO2 total vertical columns by direct-sun differential optical absorption spectroscopy].

    PubMed

    Wang, Yang; Xie, Pin-hua; Li, Ang; Xu, Jin; Zeng, Yi; Si, Fu-qi; Wu, Feng-cheng

    2012-04-01

    An appropriate reference spectrum is essential for the direct-sun differential optical absorption spectroscopy (DS-DOAS). It depends on the real reference spectrum to retrieve the total vertical column density (VCD). The spectrum detected at the time with minimum sun zenith angle under the relative clear atmospheric condition in the measurement period was conventionally selected as the reference spectrum. Because there is still untracked NO2 absorption structure in the reference spectrum, the VCD retrieved based on the above spectrum is actually relative VCD, which results in larger error. To solve this problem, a new method was investigated. A convolution of extraterrestrial high-precision solar Fraunhofer spectrum and the instrumental function of the spectrometer was computed and chosen as the reference spectrum. The error induced by NO2 absorption structure in the reference spectrum was removed. Then the fitting error of slant column density (SCD) retrieved by this method was analyzed. The correlation between the absolute SCD and the differential slant column density (dSCD) was calculated. The result shows that the error of SCD retrieved by this new method is below 1.6 x 10(16) molecules x cm(-2) on March 7, 2011, while the error generated by the normal method is about 4.25 x 10(16) molecules x cm(-2). The new method decreased more than 62% error. In addition, the results throughout the day were compared to the troposphere VCD from MAX-DOAS and they are in good agreement. It indicates that the new method could effectively reduce the VCD error of the common way. PMID:22715747

  11. Vibrational absorption and vibrational circular dichroism spectra of leucine in water under different pH conditions: Hydrogen-bonding interactions with water

    NASA Astrophysics Data System (ADS)

    Poopari, Mohammad Reza; Zhu, Peiyan; Dezhahang, Zahra; Xu, Yunjie

    2012-11-01

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy have been used to study leucine, a flexible branched-chain amino acid, in aqueous solution. The VA spectra in the range of 1800-1250 cm-1 of leucine in D2O under three representative pHs from strongly acidic (pH = 1), near neutral (pH = 6), to strongly basic (pH = 13), have been measured. The related VCD spectrum has been obtained under near neutral condition. Searches have been carried out to identify the most stable conformers of the Zwitterionic, protonated, and deprotonated forms of leucine in water. The geometry optimization, harmonic frequency calculations, and VA and VCD intensities have been computed at the B3LYP/6-311++G(d,p) level with the implicit polarizable continuum solvation model. While the observed VA spectra under three pHs can be well interpreted with the inclusion of the implicit solvation model, both implicit and explicit solvation models have been found to be crucial for the adequate interpretation of the complex VCD features observed. Molecular dynamics simulations and radial distribution functions have been used to aid the modeling of the leucine-(water)N clusters. It has been recognized that the insertion of a water molecule between the COO- and NH3+ functional groups in the explicit solvated clusters is critical to reproduce the VCD signatures observed. Furthermore, the inclusion of the implicit bulk water environment has been found to be essential to lock water molecules, which are directly hydrogen bonded to leucine, into the positions expected in solution. The application of the explicit and implicit solvation models simultaneously allows new insights into the hydrogen bonding network surrounding leucine in aqueous solution and the role of the surrounding bulk water in stabilizing such hydrogen-bonding network.

  12. Mobile MAX-DOAS observation of NO2 and comparison with OMI satellite data in the western coastal areas of the Korean peninsula.

    PubMed

    Chong, Jihyo; Kim, Young J; Gu, Myojeong; Wagner, Thomas; Song, Chul H

    2016-01-01

    Ground-based MAX-DOAS measurements have been used to retrieve column densities of atmospheric absorbers such as NO2, SO2, HCHO, and O3. In this study, mobile MAX-DOAS measurements were conducted to map the 2-D distributions of atmospheric NO2 in the western coastal areas of the Korean peninsula. A Mini-MAX-DOAS instrument was mounted on the rooftop of a mobile lab vehicle with a telescope mounted parallel to the driving direction, pointing forward. The measurements were conducted from 21 to 24 December 2010 along the western coastal areas from Gomso harbor (35.59N, 126.61E) to Gunsan harbor (35.98N, 126.67E). During mobile MAX-DOAS observations, high elevation angles were used to avoid shades from nearby obstacles. For the determination of the tropospheric vertical column density (VCD), the air mass factor (AMF) was retrieved by the so-called geometric approximation. The NO2 VCDs from 20 and 45 degree elevation angles were retrieved from mobile MAX-DOAS measurements. The tropospheric NO2 VCDs derived from mobile MAX-DOAS measurements were compared directly to those retrieved by the OMI satellite observations. Mobile MAX-DOAS VCD was in good agreement with OMI tropospheric VCD on most days. However, OMI tropospheric VCD was much higher than that of mobile MAX-DOAS on 23 December 2010. One probable reason for this difference is that OMI retrieval might overestimate NO2 VCD under haze conditions, when a pollution plume was transported over the measurement site. The mobile MAX-DOAS observations reveal much finer spatial patterns of NO2 distributions, which can provide useful information for the validation of satellite observation of atmospheric trace gases. PMID:26239513

  13. New Developments in the SCIAMACHY Level 2 Ground Processor Towards Version 7

    NASA Astrophysics Data System (ADS)

    Meringer, Markus; Noël, Stefan; Lichtenberg, Günter; Lerot, Christophe; Theys, Nicolas; Fehr, Thorsten; Dehn, Angelika; Liebing, Patricia; Gretschany, Sergei

    2016-07-01

    SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric ChartographY) aboard ESA's environmental satellite ENVISAT observed the Earth's atmosphere in limb, nadir, and solar/lunar occultation geometries covering the UV-Visible to NIR spectral range. It is a joint project of Germany, the Netherlands and Belgium and was launched in February 2002. SCIAMACHY doubled its originally planned in-orbit lifetime of five years before the communication to ENVISAT was severed in April 2012, and the mission entered its post-operational phase. In order to preserve the best quality of the outstanding data recorded by SCIAMACHY, data processors are still being updated. This presentation will highlight three new developments that are currently being incorporated into the forthcoming version 7 of ESA's operational level 2 processor: 1. Tropospheric BrO, a new retrieval based on the scientific algorithm of (Theys et al., 2011). This algorithm had originally been developed for the GOME-2 sensor and was later adapted for SCIAMACHY. The main principle of the new algorithm is to split BrO total columns, which are already an operational product, into stratospheric VCD_{strat} and tropospheric VCD_{trop} fractions. BrO VCD_{strat} is determined from a climatological approach, driven by SCIAMACHY O_3 and NO_2 observations. Tropospheric vertical column densities are then determined as difference VCD_{trop}=VCD_{total}-VCD_{strat}. 2. Improved cloud flagging using limb measurements (Liebing, 2015). Limb cloud flags are already part of the SCIAMACHY L2 product. They are currently calculated employing the scientific algorithm developed by (Eichmann et al., 2015). Clouds are categorized into four types: water, ice, polar stratospheric and noctilucent clouds. High atmospheric aerosol loadings, however, often lead to spurious cloud flags, when aerosols had been misidentified as clouds. The new algorithm will better discriminate between aerosol and clouds. It will also have a higher

  14. Identification of products from canthaxanthin oxidation.

    PubMed

    Mordi, Raphael C; Walton, John C

    2016-04-15

    Canthaxanthin is a carotenoid that lacks pro-vitamin A activity but is known to have antioxidant activity. The products of its oxidation in oxygen were found to be mainly substituted apo-carotenals and apo-carotenones. The product profile resembles that obtained in the oxidation of β-carotene, except that with canthaxanthin these products are the 4-oxo-β-apo-carotenals and 4-oxo-β-apo-carotenones. Epoxides and diepoxides were clearly identified from β-carotene oxidation but in contrast, with canthaxanthin, apart from 5,6-epoxy-canthaxanthin, which was detected at the early stage of oxidation and minor quantities of 5,6-epoxy-β-ionone and 5,6-epoxy-4-oxo-β-apo-11-carotenal, no other epoxides were detected. The identities of these products lead us to suggest that the mechanism of canthaxanthin oxidation bears significant similarity to that of β-carotene.

  15. Synthesis, reactivity and application studies for different biolubricants

    PubMed Central

    2014-01-01

    Vegetable oils have different unique properties owing to their unique chemical structure. Vegetable oils have a greater ability to lubricate and have higher viscosity indices. Therefore, they are being more closely examined as base oil for biolubricants and functional fluids. In spite of their many advantages, vegetable oils suffer from two major drawbacks of inadequate oxidative stability and poor low-temperature properties, which hinder their utilization as biolubricant base oils. Transforming alkene groups in fatty acids to other stable functional groups could improve the oxidative stability, whereas reducing structural uniformity of the oil by attaching alkyl side chains could improve the low-temperature performance. In that light, the epoxidation of unsaturated fatty acids is very interesting as it can provide diverse side chains arising from the mono- or di-epoxidation of the unsaturated fatty acid. Oxirane ring opening by an acid-catalyzed reaction with a suitable reagent provides interesting polyfunctional compounds. PMID:24612780

  16. Rubber-modified epoxies: Analysis of the phase-separation process

    SciTech Connect

    Verchere, D.; Sautereau, H.; Pascault, J.P.; Moschiar, S.M.; Riccardi, C.C.; Williams, R.J.J.

    1993-12-31

    The phase-separation process of a diepoxide based on bisphenol A diglycidyl ether cured with a cycloaliphatic diamine in the presence of an epoxy-terminated butadiene-acrylonitrile random copolymer (ETBN) was experimentally studied and theoretically simulated. The increase in the average molecular weight of the epoxy-amine polymer is shown to be the main thermodynamic factor leading to phase separation. The competition between nucleation-growth and spinodal decomposition is analyzed. Low values of interfacial tensions and polymerization rates favor the first mechanism in most cases. A secondary phase separation must occur inside the dispersed particles, leading to a segregated epoxy-amine phase. The theoretical simulation explains the increase of the average diameter of dispersed-phase particles with increasing polymerization temperature. The volume fraction of dispersed phase is the dominating factor affecting fracture toughness. 49 refs., 16 figs.

  17. A non-canonical caleosin from Arabidopsis efficiently epoxidizes physiological unsaturated fatty acids with complete stereoselectivity.

    PubMed

    Blée, Elizabeth; Flenet, Martine; Boachon, Benoît; Fauconnier, Marie-Laure

    2012-10-01

    In plants, epoxygenated fatty acids (EFAs) are constituents of oil seeds as well as defence molecules and components of biopolymers (cutin, suberin). While the pleiotropic biological activities of mammalian EFAs have been well documented, there is a paucity of information on the physiological relevance of plant EFAs and their biosynthesis. Potential candidates for EFA formation are caleosin-type peroxygenases which catalyze the epoxidation of unsaturated fatty acids in the presence of hydroperoxides as co-oxidants. However, the caleosins characterized so far, which are mostly localized in seeds, are poor epoxidases. In sharp contrast, quantitative RT-PCR analysis revealed that PXG4, a class II caleosin gene, is expressed in roots, stems, leaves and flowers of Arabidopsis. Expressed in yeast, PXG4 encodes a calcium-dependent membrane-associated hemoprotein able to catalyze typical peroxygenase reactions. Moreover, we show here that purified recombinant PXG4 is an efficient fatty acid epoxygenase, catalyzing the oxidation of cis double bonds of unsaturated fatty acids. Physiological linoleic and linolenic acids proved to be the preferred substrates for PXG4; they are oxidized into the different positional isomers of the monoepoxides and into diepoxides. An important regioselectivity was observed; the C-12,13 double bond of these unsaturated fatty acids being the least favored unsaturation epoxidized by PXG4, linolenic acid preferentially yielded the 9,10-15,16-diepoxide. Remarkably, PXG4 catalyzes exclusively the formation of (R),(S)-epoxide enantiomers, which is the absolute stereochemistry of the epoxides found in planta. These findings pave the way for the study of the functional role of EFAs and caleosins in plants. PMID:22913587

  18. A positron annihilation lifetime spectroscopic study of the corrosion protective properties of epoxy coatings

    SciTech Connect

    MacQueen, R.C.

    1992-01-01

    Positron Annihilation Lifetime Spectroscopy (PALS) was used to measure the free volume cavity sizes and free volume fractions of crosslinked epoxy coatings on steel before and after saturation with liquid water at 23[degrees]C. A direct linear relationship between the equilibrium volume fraction of water absorbed and the dry relative free volume fraction of bisphenol A epoxy coatings was found. The free volume cavity sizes and the number of free volume cavities per unit volume of these epoxies were found to decrease after water saturation. These decreases are ascribed to the occupation of 13-17% of the free volume cavities by 2-4 water molecules per cavity. The free volume cavity size of polyglycol diepoxides was found to increase after water saturation. This increase is ascribed to the expansion of the free volume cavities by water, which is substantiated by the macroscopic swelling observed in these coatings. An inverse, linear relationship between the equilibrium water uptake and the relative free volume fraction of these coatings were observed. This result coupled with the fact that less than one molecule of nitrobenzene was determined to fit into an epoxy free volume cavity, and that nitrobenzene is quite soluble in most of the epoxides, indicates that other factors besides the magnitude of the free volume fraction affect the amount of solvent absorbed by epoxy coatings. The small percentage of free volume occupied by water and the small number of water molecules capable of filling each void of the bisphenol A epoxies after water saturation correlate to the high impedance values and the good corrosion protection of these coatings, suggesting that water passes through these coatings by slow diffusion through the connected free volume cavities in the coating. Increases in the free volume cavity sizes of the polyglycol diepoxides after water saturation correlate to the low impedance and the poor corrosion protection of these coatings.

  19. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory. PMID:26480341

  20. N-Acetyl-L-alanine N'-methylamide: a density functional analysis of the vibrational absorption and vibrational circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Jalkanen, K. J.; Suhai, S.

    1996-07-01

    Ab initio 6-31G ∗ Becke 3LYP DFT optimized geometries, vibrational frequencies, vibrational absorption (VA) intensities and vibrational circular dichroism (VCD) intensities have been calculated for the eight low energy conformers of N-acetyl-L-alanine N'-methylamide (L-AANMA) in the gas phase and one conformer stabilized by the addition of four water molecules. The VA and VCD spectra are calculated with the 6-31G ∗ Becke 3LYP force fields (Hessians) and atomic polar tensors (APT); 6-31G ∗∗ RHF atomic axial tensors (AAT) for the eight gas phase structures and 6-31G ∗/6-31G RHF AAT for the L-AANMA-water complex. The VA and VCD spectra are also calculated using the 6-31G ∗ Becke 3LYP Hessians; 6-31G ∗∗ RHF APT and AAT for the eight gas phase structures and 6-31G ∗/6-31G RHF APT and AAT for the L-AANMA-water complex. The rotational strengths of the amide A, I, II, III, IV, V and VI modes found in proteins as a function of φ and ψ (for various secondary structures) are for the first time reported for an inherently optically active molecule (non-glycine model) using the 6-31G ∗∗ and 6-31G ∗/6-31G RHF DOG AAT and 6-31G ∗ Becke 3LYP Hessians and APT. This is also the first reported VCD calculation of a molecule with the solvent present. The molecule is not completely solvated, but the important hydrogen-bonded interactions are present and the feasibility of the calculation of the Hessian, APT and AAT with solvent molecules present is demonstrated. The VA and VCD spectra are compared to the experimental VA and VCD spectra in the literature and the conformational analysis (CA) and vibrational assignment of L-AANMA are reinvestigated. The rotational strengths of the amide modes for the various conformers are also compared to peptide and protein VCD spectra of molecules with known secondary structures. The agreement between the calculated rotational strengths of the various amide modes for which experimental measurements have been made is very good

  1. A Comparative Analysis of Phase-Change Wastewater Processing Approaches for Microgravity

    NASA Technical Reports Server (NTRS)

    Lange, Kevin

    2016-01-01

    Two phase-change wastewater processing candidates, the ISS Vapor Compression Distillation (VCD) System and the Cascade Distiller System (CDS), are compared based on dynamic modeling of both technologies. Differences in fluid handling and energy recovery for the technologies are described and contrasted. Model predictions are presented showing how temperatures, pressures, and compositions vary locally within each distiller. These dynamic variations are difficult to observe experimentally and have implications regarding non-condensable buildup and salt precipitation potential. Alternative architectures involving VCD and CDS components are analyzed in terms of predicted performance and equivalent system mass (ESM). The addition of a downstream brine processor to increase water recovery is also evaluated. Options for reducing overall ESM are discussed, including the possibility of developing a single precipitation-tolerant primary wastewater processor.

  2. Vapor compression distillation module

    NASA Technical Reports Server (NTRS)

    Nuccio, P. P.

    1975-01-01

    A Vapor Compression Distillation (VCD) module was developed and evaluated as part of a Space Station Prototype (SSP) environmental control and life support system. The VCD module includes the waste tankage, pumps, post-treatment cells, automatic controls and fault detection instrumentation. Development problems were encountered with two components: the liquid pumps, and the waste tank and quantity gauge. Peristaltic pumps were selected instead of gear pumps, and a sub-program of materials and design optimization was undertaken leading to a projected life greater than 10,000 hours of continuous operation. A bladder tank was designed and built to contain the waste liquids and deliver it to the processor. A detrimental pressure pattern imposed upon the bladder by a force-operated quantity gauge was corrected by rearranging the force application, and design goals were achieved. System testing has demonstrated that all performance goals have been fulfilled.

  3. Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

    SciTech Connect

    Scherrer, Arne; Agostini, Federica; Gross, E. K. U.; Sebastiani, Daniel; Vuilleumier, Rodolphe

    2015-08-21

    The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similar to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

  4. Helical polyurethane@attapulgite nanocomposite: Preparation, characterization and study of optical activity

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Zhou, Yuming; Sun, Yanqing; Fan, Kai; Guo, Xingxing; Jiang, Xiaolei

    2009-08-01

    Helical polyurethane@attapulgite (BM-ATT) based on R-1,1'-binaphthyl-2',2-diol (R-BINOL) composite was prepared after the surface modification of attapulgite (ATT). BM-ATT was characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HTEM) and vibrational circular dichroism (VCD) spectroscopy. FT-IR and XRD analyses indicate that the helical polyurethane has been successfully grafted onto the surfaces of the modified ATT without destroying the original crystalline structure of ATT. BM-ATT exhibits the rod-like structure by SEM, TEM, and HTEM photographs. BM-ATT displays obvious Cotton effect for some absorbance in VCD spectrum, and its optical activity results from the singlehanded conformation of helical polyurethane.

  5. [The retrieval of ozone column densities by passive differential optical absorption spectroscopy during summer at Zhongshan Station, Antarctic].

    PubMed

    Luo, Yu-Han; Liu, Wen-Qing; Bian, Lin-Gen; Lu, Chang-Gui; Xie, Pin-Hua; Si, Fu-Qi; Sun, Li-Guang

    2011-02-01

    Daily ozone column densities were monitored by Passive DOAS (differential optical absorption spectroscopy) from December 10th, 2008 to Feb 19th, 2009 at Zhongshan Station, Antarctic (69 degrees 22'24" S, 76 degrees 22'14" E). Considering the absorption of O3, OClO, NO2, O4, BrO and the Ring effect, ozone slant column densities were retrieved using the zenith scattered sunlight as the light source. The results showed that there was no obvious "ozone hole" during the monitoring period, but ozone VCD (vertical column density) had greatly changed within short time scale, especially in middle December and early February. The analysis of passive DOAS and Brewer measurements of ozone VCD showed good agreement with the correlative coefficient of 0.863, while satellite board OMI measurements with the correlative coefficient of 0.840, which confirmed the validity of the monitoring of Passive DOAS. PMID:21510403

  6. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory.

  7. Optimized interferometric setup for chiral and achiral ultrafast IR spectroscopy.

    PubMed

    Dutta, Biplab; Helbing, Jan

    2015-06-15

    We report an actively stabilized interferometer-based set-up for the detection of vibrational circular dichroism (VCD) and optical rotatory dispersion (VORD) with femtosecond laser pulses. Our approach combines and improves elements of several previous measurement strategies, including signal amplification in a crossed polarizer configuration, precise control and modulation of polarization, phase stability, tight focusing, broad-band detection and spectral interferometry. Their importance for static and transient measurements is motivated by a signal analysis based on Jones matrices and response theory. Only depending on the pump-beam polarization, the set-up can selectively detect transient VCD and VORD or transient linear birefringence (LB) and linear dichroism (LD), which usually constitute the dominant artifacts in the chiral measurements. For illustration we present transient LB and LD data of an achiral Rhenium carbonyl complex, detected simultaneously by spectral interferometry, and we analyze residual background signals in the experimental configuration for transient chiral spectroscopy. PMID:26193616

  8. Hypnosis for Asthma and Vocal Cord Dysfunction in a Patient With Autism.

    PubMed

    Kaslovsky, Robert; Gottsegen, David

    2015-10-01

    Wheezing in children often is the result of asthma, but vocal cord dysfunction (VCD) may cause stridor or sounds that sometimes are misattributed to the wheezing of asthma. The frequent comorbidity of asthma and VCD also adds to the difficulty in making a clear diagnosis. The challenges of evaluating and treating wheezing are complicated further in children with developmental disorders, such as autism, because of the difficulties of obtaining an adequate history and assessing the clinical response to treatment. This article presents a patient with multiple psychiatric problems, including autism, with severe recurrent wheezing as a result of vocal cord dysfunction and asthma. Hypnosis has previously proven efficacious for treating vocal cord dysfunction, and in this case, hypnotic techniques were major factors in successful symptom control.

  9. Crystallization of an achiral cyclohexanone ethylene ketal in enantiomorphs and determination of the absolute structure.

    PubMed

    Graus, Sara; Tejedor, Rosa M; Uriel, Santiago; Serrano, José Luis; Alkorta, Ibon; Elguero, José

    2010-06-16

    The achiral 4-methoxy-4-(p-methoxyphenyl)-cyclohexanone ethylene ketal (1) resolves spontaneously. The crystal structure is solved in chiral spatial group P2(1). Because compound 1 is composed of only light atoms (C, H, O) it is not possible to determine its absolute structure configuration. An efficient procedure for the absolute structure configuration determination of flexible molecules containing only light atoms is proposed, based on the combination of X-ray diffraction, solid-state VCD, and DFT calculations.

  10. Tetravalent Dengue Vaccine: A Review in the Prevention of Dengue Disease.

    PubMed

    Scott, Lesley J

    2016-09-01

    Tetravalent, live-attenuated, dengue vaccine (Dengvaxia(®); CYD-TDV) is the first vaccine approved for the prevention of dengue disease caused by dengue virus (DENV) serotypes 1-4 in individuals aged 9-45 or 9-60 years living in high dengue endemic areas. This narrative review discusses the immunogenicity, protective efficacy, reactogenicity and safety of CYD-TDV in the prevention of dengue disease. In Latin American and Asian phase 3 trials in children and adolescents (n > 30,000), the recommended three-dose CYD-TDV regimen was efficacious in preventing virologically-confirmed dengue (VCD) during the period from 28 days after the last dose (month 13) to month 25, meeting the primary endpoint criteria. Protective efficacy against VCD in the respective individual trials was 60.8 and 56.5 % (primary analysis). During the 25-month active surveillance phase, CYD-TDV also provided protective efficacy against VCD, severe dengue, any grade of dengue haemorrhagic fever and VCD-related hospitalization in children aged 9 years and older. CYD-TDV was generally well tolerated, with no safety concerns identified after up to 4 years' follow-up (i.e. from post dose 1) in ongoing long-term studies. Based on evidence from the dengue clinical trial program, the WHO SAGE recommended that countries with high dengue endemicity consider introducing CYD-TDV as part of an integrated disease prevention strategy to lower disease burden. Pharmacoeconomic considerations will be pivotal to implementing dengue vaccination prevention strategies in these countries. The availability of a dengue vaccine is considered essential if the 2012 WHO global strategy targets for reducing the burden of dengue disease by 2020 are to be attained. Hence, CYD-TDV represents a major advance for the prevention of dengue disease in high dengue endemic regions. PMID:27506852

  11. Satellite-observed NO2, SO2, and HCHO Vertical Column Densities in East Asia: Recent Changes and Comparisons with Regional Model

    NASA Astrophysics Data System (ADS)

    Kim, H. C.; Lee, P.; Kim, S.; Mok, J.; Yoo, H. L.; Bae, C.; Kim, B. U.; Lim, Y. K.; Woo, J. H.; Park, R.

    2015-12-01

    This study reports the recent changes in tropospheric NO2, SO2, and HCHO vertical column densities (VCD) in East Asia observed from multiple satellites, highlighting especially the annual trend changes of NO2 and SO2 over Beijing-Tianjin-Hebei (BTH) region of China since 2010. Tropospheric VCD data from Global Ozone Monitoring Experiment (GOME), SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY), Ozone Monitoring Instrument (OMI) and GOME-2, retrieved from the Royal Netherlands Meteorological Institute (KNMI) and OMI National Aeronautics and Space Administration (NASA) standard products, are utilized to investigate the annual trends of NO2, SO2, and HCHO VCDs from 2001 to 2015. They are also compared with simulations from Community Multi-scale Air Quality Model (CMAQ) based forecast system by the Integrated Multi-scale Air Quality System for Korea (IMAQS-K) of Ajou University. Until 2011, the changes in NO2 VCD over East Asian countries agree well with the findings of previous research, including the impact of the economic downturn during 2008-2009 and the subsequent quick recovery in China. After peaking in 2011, the NO2 VCD observations from active instruments (OMI and GOME-2) over China started to show a slower decreasing trend, mostly led by the rapid changes in the BTH region in northern China. On the other hand, SO2 started to decline earlier, from 2007, but inclined back from 2010 to 2012, and then back to declining trend since 2012. While satellite observations show dramatic recent changes, the model could not reproduce those changes mostly due to its use of fixed emission inventory. We conclude that rapid update of latest emission inventory is necessary for an accurate forecast of regional air quality in east Asia, especially for upcoming international sports events in PyeongChang (Korea), Tokyo (Japan) and Beijing (China) in 2018, 2020 and 2022, respectively.

  12. Spectroscopic investigation of Ginkgo biloba terpene trilactones and their interaction with amyloid peptide Aβ(25-35)

    NASA Astrophysics Data System (ADS)

    He, Jiangtao; Petrovic, Ana G.; Dzyuba, Sergei V.; Berova, Nina; Nakanishi, Koji; Polavarapu, Prasad L.

    2008-04-01

    The beneficial effects of Ginkgo biloba extract in the "treatment" of dementia are attributed to its terpene trilactone (TTL) constituents. The interactions between TTLs and amyloid peptide are believed to be responsible in preventing the aggregation of peptide. These interactions have been investigated using infrared vibrational absorption (VA) and circular dichroism (VCD) spectra. Four TTLs, namely ginkgolide A (GA), ginkgolide B (GB), ginkgolide C (GC) and bilobalide (BB) and amyloid Aβ(25-35) peptide, as a model for the full length peptide, are used in this study. GA-monoether and GA-diether have also been synthesized and investigated to help understand the role of individual carbonyl groups in these interactions. The precipitation and solubility issues encountered with the mixture of ginkgolide + Aβ peptide for VA and VCD studies were overcome using binary ethanol-D 2O solvent mixture. The experimental VA and VCD spectra of GA, GB, GC and BB, GA-monoether and GA-diether have been analyzed using the corresponding spectra predicted with density functional theory. The time-dependent experimental VA and VCD spectra of Aβ(25-35) peptide and the corresponding experimental spectra in the presence of TTLs indicated that the effect of the TTLs in modulating the aggregation of Aβ(25-35) peptide is relatively small. Such small effects might indicate the absence of a specific interaction between the TTLs and Aβ(25-35) peptide as a major force leading to the reduced aggregation of amyloid peptides. It is possible that the therapeutic effect of G. biloba extract does not originate from direct interactions between TTLs and the Aβ(25-35) peptide and is more complex.

  13. Measurements of formaldehyde total content in troposphere using DOAS technique in Moscow Region

    NASA Astrophysics Data System (ADS)

    Borovski, A. N.; Dzhola, A. V.; Grechko, E. I.; Postylyakov, O. V.; Ivanov, V. A.; Kanaya, Y.

    2015-11-01

    Formaldehyde (HCHO) in the atmosphere is a product of oxidation of methane and other volatile organic compounds (VOCs), and so its content is an important index of air pollution by VOCs. HCHO has strong absorption cross-section in the UV spectral region and, hence, HCHO vertical column density (VCD) can be measured by remote optical methods including differential optical absorption spectroscopy (DOAS). Spectral measurements of scattered solar radiation are performed at Zvenigorod Scientific Station (ZSS, 55°41'49''N, 36°46'29''E) located in 38 km west from Moscow Ring Road by MAX-DOAS instrument since 2008. For analysis of the HCHO variability we selected spectra taken in cloud free conditions. Version 1.2 of retrieval algorithm is used. It uses information on the surface albedo and the height of the atmospheric boundary layer inferred from a model. Data screening using color index was implemented. The obtained data quantify the Moscow megapolis influence on air quality at Zvenigorod by comparison of HCHO VCD for east and west wind directions. HCHO VCD for east winds is grater one for west winds for 0.5×1016 mol×cm-2 in average. Strong dependence of HCHO VCD on air temperature is noticeable in our data for air temperatures from +5 to +35°C. In different conditions of the atmosphere gradient of the temperature effect is about 1.1-1.2×1015 mol×cm-2×°C-1. The increase of the formaldehyde content with the increase of the air temperature can be caused by the HCHO formation from non-methane biogenic volatile organic compounds for which more emission is expected at higher temperatures.

  14. Organocatalytic asymmetric addition of malonates to unsaturated 1,4-diketones

    PubMed Central

    Žari, Sergei; Kailas, Tiiu; Kudrjashova, Marina; Öeren, Mario; Järving, Ivar; Tamm, Toomas; Lopp, Margus

    2012-01-01

    Summary The organocatalytic Michael addition of malonates to symmetric unsaturated 1,4-diketones catalyzed by thiourea and squaramide derivatives with Cinchona alkaloids afforded the formation of a new C–C bond in high yields (up to 98%) and enantiomeric purities (up to 93%). The absolute configuration of the product was suggested from comparison of the experimental and calculated VCD spectra of the reaction product 3a. PMID:23019480

  15. On Quark Mixings and CKM Matrix

    NASA Astrophysics Data System (ADS)

    Senju, H.

    1991-05-01

    Inspired by unique features of the preon-subpreon model, we study quark mixings and the CKM matrix. The resultant CKM matrix has very nice properties. V_{cb} =~ - V_{ts} is predicted. Our scheme has a strong possibility to explain that V_{us} and V_{cd} are remarkably large compared with other off-diagonal elements and that V_{ub} and V_{td} are much smaller than V_{cb}.

  16. Spectroscopic investigation of the structures of dialkyl tartrates and their cyclodextrin complexes.

    PubMed

    Zhang, Peng; Polavarapu, Prasad L

    2007-02-01

    Structures of three dialkyl tartrates, namely, dimethyl tartrate, diethyl tartrate, and diisopropyl tartrate, in CCl4, dimethyl sulfoxide (DMSO)/DMSO-d6, and H2O/D2O solvents have been investigated using vibrational absorption (VA), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD). VA, VCD, and ORD spectra are found to be dependent on the solvent used. Density functional theory (DFT) calculations are used to interpret the experimental data in CCl4 and DMSO. The trans-COOR conformer with hydrogen bonding between the OH group and the C=O group attached to the same chiral carbon is dominant for dialkyl tartrates both in vacuum and in CCl4. The experimental VA, VCD, and ORD data of dialkyl-D-tartrates in CCl4 correlated well with those predicted for dimethyl-(S,S)-tartrate molecule as both isolated and solvated in CCl4. In DMSO solvent, dialkyl tartrate molecules favor formation of intermolecular hydrogen bonding with DMSO molecules. Clusters of dimethyl-(S,S)-tartrate, with one molecule of dimethyl-(S,S)-tartrate hydrogen bonded to two DMSO molecules, are used for the DFT calculations. A trans-COOR cluster and a trans-H cluster are needed to obtain a reasonable agreement between the predicted and experimental data of dimethyl tartrate in DMSO solvent. VA, VCD, and optical rotations are also measured for dialkyl tartrate-cyclodextrin complexes. It is noted that these properties are barely affected by complexation of dialkyl tartrates with cyclodextrins, indicating weak interaction between tartrates and cyclodextrin. Binding constants of alpha-CD and beta-CD with diethyl L-tartrate in both H2O and DMSO have been determined using isothermal titration calorimetry technique. The smaller binding constants (less than 100) confirmed the weak interaction between tartrates and cyclodextrin in the solution state.

  17. Metal-Organic Frameworks with Achiral/Monochiral Nano-channels

    SciTech Connect

    Yi, Xiao Yi; Fang, Hua-Cai; Gu, Zhi-Gang; Zhou, Zheng-Yuan; Cai, Yue-Peng; Tian, Jian; Thallapally, Praveen K.

    2011-07-01

    Two dimensional layered like coordination polymer [Co(2,4'-bpdc)(H2O)]n containing one-dimensional double-stranded left-handed helical channels from achiral building block 2,4'-biphenyldicarboxylic acid (2,4'-H2bpdc) was reported. The resultant crystals were not racemic as evidenced by the observation of strong signals in vibrational circular dichroism (VCD) and circular dichroism (CD) spectra

  18. Diagnostic accuracy of self-reported symptomatic assessment versus per speculum/per vaginal examination for the diagnosis of vaginal/cervical discharge and lower abdominal pain syndromes among female sex workers

    PubMed Central

    Kosambiya, Jayendrakumar K.; Baria, H. G.; Parmar, Rohit; Mhaskar, Rahul; Emmanuel, Patricia; Kumar, Ambuj

    2016-01-01

    Background: National AIDS Control Organization guidelines on enhanced syndromic case management of sexually transmitted infections (STIs) and reproductive tract infections (RTIs) require per speculum (P/S) and per vaginal (P/V) examinations for diagnosis of STIs. However, it is not known if the addition of P/S and P/V examinations to self-reported symptomatic assessment adds any value for the diagnosis of STI/RTI. Objective: To assess the diagnostic accuracy of P/S and P/V examinations compared with self-reported symptomatic assessment in a cohort of female sex workers (FSWs). Methods: We performed a cross-sectional study from August 2009 to June 2010, among 519 FSWs in Surat city, Gujarat, India. Symptomatic assessment for the presence or absence of vaginal/cervical discharge (VCD) or lower abdominal pain (LAP) was done using a self-administered questionnaire. After completion of the questionnaire, all participants underwent P/S and P/V examinations. Summary diagnostic accuracy measures were calculated. Results: Five hundred and nineteen FSWs between the ages of 18–49 years participated in the study. The median age of participants was 31 years. The prevalence of VCD and LAP syndromes based on vaginal discharge, LAP, or both was 56%, 5,–10%, respectively. The sensitivity of P/S and P/V examinations depending on symptomatic assessment ranged from 47% to 76%. The specificity ranged from 73% to 93%. The positive predictive value ranged from 25% to 83%, and the negative predictive value ranged from 56% to 98%. Conclusion: Symptomatic assessment alone is not adequate for the diagnosis of VCD and LAP syndromes and can lead to a significant number of missed cases (36%). A P/S and P/V examinations is critical for assessment of VCD and LAP syndromes and subsequent treatment. PMID:27190406

  19. IR and Vibrational Circular Dichroism Spectroscopy of Matrine- and Artemisinin-Type Herbal Products: Stereochemical Characterization and Solvent Effects.

    PubMed

    Zhang, Yuefei; Poopari, M Reza; Cai, Xiaoli; Savin, Aliaksandr; Dezhahang, Zahra; Cheramy, Joseph; Xu, Yunjie

    2016-04-22

    Five Chinese herbal medicines--matrine, oxymatrine, sophoridine, artemisinin, and dihydroartemisinin--were investigated using vibrational circular dichroism (VCD) experiments and density functional theory calculations to extract their stereochemical information. The three matrine-type alkaloids are available from the dry roots of Sophora flavescens and have long been used in various traditional Chinese herbal medicines to combat diseases such as cancer and cardiac arrhythmia. Artemisinin and the related dihydroartemisinin, discovered in 1979 by Professor Youyou Tu, a 2015 Nobel laureate in medicine, are effective drugs for the treatment of malaria. The VCD measurements were carried out in CDCl3 and DMSO-d6, two solvents with different dielectric constants and hydrogen-bonding characteristics. A "clusters-in-a-liquid" approach was used to model both explicit and implicit solvent effects. The studies show that effectively accounting for solvent effects is critical to using IR and VCD spectroscopy to provide unique spectroscopic features to differentiate the potential stereoisomers of these Chinese herbal medicines. PMID:27070079

  20. Comparative Analysis of IR and Vibrational Circular Dichroism Spectra for a Series of Camphor-Related Molecules

    NASA Astrophysics Data System (ADS)

    Abbate, Sergio; Burgi, Luigi Filippo; Gangemi, Fabrizio; Gangemi, Roberto; Lebon, France; Longhi, Giovanna; Pultz, Vaughan M.; Lightner, David A.

    2009-09-01

    The absorption spectra and vibrational circular dichroism (VCD) spectra in the mid-IR range 1600-950 cm-1 of 10 camphor-related compounds have been recorded and compared to DFT calculated spectra at the B3PW91/TZ2P level and have been examined together with the corresponding data of the parent molecules. The rigidity of the bridged structure common to all compounds investigated permits (a) identification of three spectroscopic regions in the mid-IR range that can be "used" separately by the interested stereochemist for structural diagnosis and assignment of some major characteristics of the VCD spectra in these regions to what we call "skeletal chiral sense" and (b) recognition of possible conformers for flexible substituent groups, when present. VCD spectra of the 10 molecules have been recorded and analyzed also in the CH-stretching region, 3100-2800 cm-1. Here, we have been able to identify and characterize features of vibrational excitons by comparison of data within the 10-molecule class. To find a theoretical justification of result (a), we have examined the potential energy distribution of the normal modes in the mid-IR range, the partitioning of the calculated rotational strengths in terms of contributions from all couples of internal coordinates, the angle formed by the two vectors, the electric dipole transition moment and the magnetic dipole transition moment, and finally the overlap of normal modes of different molecules. A discussion is provided as to the usability of the introduced algorithms.

  1. IR and Vibrational Circular Dichroism Spectroscopy of Matrine- and Artemisinin-Type Herbal Products: Stereochemical Characterization and Solvent Effects.

    PubMed

    Zhang, Yuefei; Poopari, M Reza; Cai, Xiaoli; Savin, Aliaksandr; Dezhahang, Zahra; Cheramy, Joseph; Xu, Yunjie

    2016-04-22

    Five Chinese herbal medicines--matrine, oxymatrine, sophoridine, artemisinin, and dihydroartemisinin--were investigated using vibrational circular dichroism (VCD) experiments and density functional theory calculations to extract their stereochemical information. The three matrine-type alkaloids are available from the dry roots of Sophora flavescens and have long been used in various traditional Chinese herbal medicines to combat diseases such as cancer and cardiac arrhythmia. Artemisinin and the related dihydroartemisinin, discovered in 1979 by Professor Youyou Tu, a 2015 Nobel laureate in medicine, are effective drugs for the treatment of malaria. The VCD measurements were carried out in CDCl3 and DMSO-d6, two solvents with different dielectric constants and hydrogen-bonding characteristics. A "clusters-in-a-liquid" approach was used to model both explicit and implicit solvent effects. The studies show that effectively accounting for solvent effects is critical to using IR and VCD spectroscopy to provide unique spectroscopic features to differentiate the potential stereoisomers of these Chinese herbal medicines.

  2. Analysis of sagittal balance using spinopelvic parameters in ankylosing spondylitis patients treated with vertebral column decancellation surgery.

    PubMed

    Lin, Bin; Zhang, Wen-Bin; Cai, Tao-yi; Lu, Cheng-Wu; Zhou, Qin; Huang, Zhuanzhi; Yu, Hui

    2015-09-01

    This study was designed to explore the change of spinopelvic parameters after vertebral column decancellation (VCD) for the management of thoracolumbar kyphosis secondary to ankylosing spondylitis (AS). Forty-two AS patients including thirty-six males and six females with thoracolumbar kyphosis, who underwent VCD from April 2005 to June 2012 in our hospital, were retrospectively reviewed. A series of spinopelvic parameters including thoracic kyphosis (TK), lumbar lordosis (LL), sacral slope (SS), pelvic incidence (PI), pelvic tilt (PT) and sagittal vertical axis (SVA) measured on preoperative and postoperative free-standing radiographs were obtained and analyzed. Also clinical assessments were performed with the Oswestry disability index (ODI) and the Bath Ankylosing Spondylitis Activity and Function Index (BASDAI and BASFI) so as to seek correlations between radiological parameters and symptoms. Except for pelvic incidence (PI), significant difference was found in all radiological spinopelvic parameters between the preoperative and follow-up values. Furthermore, there was significant improvement in the clinical assessment parameters ODI, BASDAI and BASFI, which all correlated significantly with the postoperative pelvic tilt (PT). The results of this study show that posterior VCD is an effective option to manage sagittal imbalance in AS. In the current series, patients improving LL and PT were found to achieve good clinical outcomes. Overall, our findings show that it is important to quantify sagittal spinopelvic parameters and promote sagittal balance in the surgery for AS. PMID:26435251

  3. Amide I vibrational circular dichroism of polypeptides: Generalized fragmentation approximation method

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Kim, Joong-Soo; Cho, Minhaeng

    2005-05-01

    Fragment analyses of vibrational circular dichroic response of dipeptides were carried out recently [Choi and Cho, J. Chem. Phys. 120, 4383 (2004)]. In the present paper, by using a minimal size unit peptide containing two chiral carbons covalently bonded to the peptide group, a generalized fragmentation approximation method is discussed and applied to the calculations of infrared-absorption and vibrational circular dichroism (VCD) intensities of amide I vibrations in various secondary structure polypeptides. Unlike the dipole strength determining IR-absorption intensity, the rotational strength is largely determined by the cross terms that are given by the inner product between the transition electric dipole and the transition magnetic dipole of two different peptides. This explains why the signs and magnitudes of VCD peaks are far more sensitive to the relative orientation and distance between different peptide bonds in a given protein. In order to test the validity of fragmentation approximation, three different segments in a globular protein ubiquitin, i.e., right-handed α-helix, β-sheet, and β-turn regions, were chosen for density-functional theory (DFT) calculations of amide I vibrational properties and the numerically simulated IR-absorption and VCD spectra by using the fragmentation method are directly compared with DFT results. It is believed that the fragmentation approximation method will be of use in numerically simulating vibrational spectra of proteins in solutions.

  4. OMI NO2 column densities over North American urban cities: the effect of satellite footprint resolution

    NASA Astrophysics Data System (ADS)

    Kim, H. C.; Lee, P.; Judd, L.; Pan, L.; Lefer, B.

    2015-10-01

    Nitrogen dioxide vertical column density (NO2 VCD) measurements via satellite are compared with a fine-scale regional chemistry transport model, using a new approach that considers varying satellite footprint sizes. Space-borne NO2 VCD measurement has been used as a proxy for surface nitrogen oxide (NOx) emission, especially for anthropogenic urban emission, so accurate comparison of satellite and modeled NO2 VCD is important in determining the future direction of NOx emission policy. The National Aeronautics and Space Administration Ozone Monitoring Instrument (OMI) NO2 VCD measurements, retrieved by the Royal Netherlands Meteorological Institute (KNMI), are compared with a 12 km Community Multi-scale Air Quality (CMAQ) simulation from the National Oceanic and Atmospheric Administration. We found that OMI footprint pixel sizes are too coarse to resolve urban NO2 plumes, resulting in a possible underestimation in the urban core and overestimation outside. In order to quantify this effect of resolution geometry, we have made two estimates. First, we constructed pseudo-OMI data using fine-scale outputs of the model simulation. Assuming the fine-scale model output is a true measurement, we then collected real OMI footprint coverages and performed conservative spatial regridding to generate a set of fake OMI pixels out of fine-scale model outputs. When compared to the original data, the pseudo-OMI data clearly showed smoothed signals over urban locations, resulting in roughly 20-30 % underestimation over major cities. Second, we further conducted conservative downscaling of OMI NO2 VCD using spatial information from the fine-scale model to adjust the spatial distribution, and also applied Averaging Kernel (AK) information to adjust the vertical structure. Four-way comparisons were conducted between OMI with and without downscaling and CMAQ with and without AK information. Results show that OMI and CMAQ NO2 VCDs show the best agreement when both downscaling and AK

  5. Infrared optical activity: electric field approaches in time domain.

    PubMed

    Rhee, Hanju; Choi, Jun-Ho; Cho, Minhaeng

    2010-12-21

    Vibrational circular dichroism (VCD) spectroscopy provides detailed information about the absolute configurations of chiral molecules including biomolecules and synthetic drugs. This method is the infrared (IR) analogue of the more popular electronic CD spectroscopy that uses the ultraviolet and visible ranges of the electromagnetic spectrum. Because conventional electronic CD spectroscopy measures the difference in signal intensity, problems such as weak signal and low time-resolution can limit its utility. To overcome the difficulties associated with that approach, we have recently developed femtosecond IR optical activity (IOA) spectrometry, which directly measures the IOA free-induction-decay (FID), the impulsive chiroptical IR response that occurs over time. In this Account, we review the time-domain electric field measurement and calculation methods used to simultaneously characterize VCD and related vibrational optical rotatory dispersion (VORD) spectra. Although conventional methods measure the electric field intensity, this vibrational technique is based on a direct phase-and-amplitude measurement of the electric field of the chiroptical signal over time. This method uses a cross-polarization analyzer to carry out heterodyned spectral interferometry. The cross-polarization scheme enables us to selectively remove the achiral background signal, which is the dominant noise component present in differential intensity measurement techniques. Because we can detect the IOA FID signal in a phase-amplitude-sensitive manner, we can directly characterize the time-dependent electric dipole/magnetic dipole response function and the complex chiral susceptibility that contain information about the angular oscillations of charged particles. These parameters yield information about the VCD and VORD spectra. In parallel with such experimental developments, we have also calculated the IOA FID signal and the resulting VCD spectrum. These simulations use a quantum mechanical

  6. Infrared optical activity: electric field approaches in time domain.

    PubMed

    Rhee, Hanju; Choi, Jun-Ho; Cho, Minhaeng

    2010-12-21

    Vibrational circular dichroism (VCD) spectroscopy provides detailed information about the absolute configurations of chiral molecules including biomolecules and synthetic drugs. This method is the infrared (IR) analogue of the more popular electronic CD spectroscopy that uses the ultraviolet and visible ranges of the electromagnetic spectrum. Because conventional electronic CD spectroscopy measures the difference in signal intensity, problems such as weak signal and low time-resolution can limit its utility. To overcome the difficulties associated with that approach, we have recently developed femtosecond IR optical activity (IOA) spectrometry, which directly measures the IOA free-induction-decay (FID), the impulsive chiroptical IR response that occurs over time. In this Account, we review the time-domain electric field measurement and calculation methods used to simultaneously characterize VCD and related vibrational optical rotatory dispersion (VORD) spectra. Although conventional methods measure the electric field intensity, this vibrational technique is based on a direct phase-and-amplitude measurement of the electric field of the chiroptical signal over time. This method uses a cross-polarization analyzer to carry out heterodyned spectral interferometry. The cross-polarization scheme enables us to selectively remove the achiral background signal, which is the dominant noise component present in differential intensity measurement techniques. Because we can detect the IOA FID signal in a phase-amplitude-sensitive manner, we can directly characterize the time-dependent electric dipole/magnetic dipole response function and the complex chiral susceptibility that contain information about the angular oscillations of charged particles. These parameters yield information about the VCD and VORD spectra. In parallel with such experimental developments, we have also calculated the IOA FID signal and the resulting VCD spectrum. These simulations use a quantum mechanical

  7. Measurements of tropospheric NO2 in Romania using a zenith-sky mobile DOAS system and comparisons with satellite observations.

    PubMed

    Constantin, Daniel-Eduard; Merlaud, Alexis; Van Roozendael, Michel; Voiculescu, Mirela; Fayt, Caroline; Hendrick, François; Pinardi, Gaia; Georgescu, Lucian

    2013-01-01

    In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 10(15) molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 10(15) molec./cm2 (GOME-2) and (3.2 ± 3.2) × 10(15) molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 10(15) molec./cm2. Average ground measurements over "clean areas", on 18 July 2011, give (2.5 ± 0.6) × 10(15) molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 10(15) molec./cm2. PMID:23519349

  8. Measurements of Tropospheric NO2 in Romania Using a Zenith-Sky Mobile DOAS System and Comparisons with Satellite Observations

    PubMed Central

    Constantin, Daniel-Eduard; Merlaud, Alexis; Van Roozendael, Michel; Voiculescu, Mirela; Fayt, Caroline; Hendrick, François; Pinardi, Gaia; Georgescu, Lucian

    2013-01-01

    In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 1015 molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 1015 molec./cm2 (GOME-2) and (3.2 ± 3.2) × 1015 molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 1015 molec./cm2. Average ground measurements over “clean areas”, on 18 July 2011, give (2.5 ± 0.6) × 1015 molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 1015 molec./cm2. PMID:23519349

  9. Study of thermally reworkable epoxy materials and thermal conductivity enhancement using carbon fiber for electronics packaging

    NASA Astrophysics Data System (ADS)

    Li, Haiying

    Epoxy resins are widely used as the underfill materials for the integrated circuit (IC) chips for the reliability enhancement and as the binder of electrically conductive adhesives (ECA). However, cured epoxy materials are infusible and insoluble networks which is a problem for the repair of a printed circuit board assembly packaged with epoxy materials. In this study, six diepoxides containing aromatic moieties and low temperature degradable linkages, secondary and tertiary benzoates, and carbonates, were synthesized and characterized. Underfills based on four of these epoxides were developed and evaluated respect to their properties and reworkabilility. One of the reworkable underfills was evaluated with the 85°C/85% relative humidity test as the underfill of several ball-grid-array components on a organic board, which showed a high enhanced reliability. Underfill materials based on a synthesized bisphenol-A diepoxide were developed for the no-flow underfill process and were evaluated regarding the application on both tin/lead and lead-free solders. The latent curing mechanism of the catalyst and the influence of fluxing agents were studied. The reworkable underfills showed satisfying overall properties on both Sn/Pb and Sn/Ag/Cu solders. A unique approach for solving the problem of low reliability of ECAs was demonstrated. Small amount of sacrificial metal and alloy powders were added in silver flake based ECA and applied on six pad surfaces. The aging of bulk resistivity and contact resistance of ECA/metal surface pairs were studied and two alloys stabilized the contact resistance on all tested metal surfaces. The internal heat generation of IC devices quickly increases which leads to deteriorated performance and low reliability. The thermally insulating property of polymeric underfills make this even worse with slow heat dissipation. In this study, a carbon fiber of high thermal conductivity was used together with silica in epoxy underfill materials and a 300

  10. Use of a small molecule cell cycle inhibitor to control cell growth and improve specific productivity and product quality of recombinant proteins in CHO cell cultures

    PubMed Central

    Du, Zhimei; Treiber, David; McCarter, John D; Fomina-Yadlin, Dina; Saleem, Ramsey A; McCoy, Rebecca E; Zhang, Yuling; Tharmalingam, Tharmala; Leith, Matthew; Follstad, Brian D; Dell, Brad; Grisim, Brent; Zupke, Craig; Heath, Carole; Morris, Arvia E; Reddy, Pranhitha

    2015-01-01

    The continued need to improve therapeutic recombinant protein productivity has led to ongoing assessment of appropriate strategies in the biopharmaceutical industry to establish robust processes with optimized critical variables, that is, viable cell density (VCD) and specific productivity (product per cell, qP). Even though high VCD is a positive factor for titer, uncontrolled proliferation beyond a certain cell mass is also undesirable. To enable efficient process development to achieve consistent and predictable growth arrest while maintaining VCD, as well as improving qP, without negative impacts on product quality from clone to clone, we identified an approach that directly targets the cell cycle G1-checkpoint by selectively inhibiting the function of cyclin dependent kinases (CDK) 4/6 with a small molecule compound. Results from studies on multiple recombinant Chinese hamster ovary (CHO) cell lines demonstrate that the selective inhibitor can mediate a complete and sustained G0/G1 arrest without impacting G2/M phase. Cell proliferation is consistently and rapidly controlled in all recombinant cell lines at one concentration of this inhibitor throughout the production processes with specific productivities increased up to 110 pg/cell/day. Additionally, the product quality attributes of the mAb, with regard to high molecular weight (HMW) and glycan profile, are not negatively impacted. In fact, high mannose is decreased after treatment, which is in contrast to other established growth control methods such as reducing culture temperature. Microarray analysis showed major differences in expression of regulatory genes of the glycosylation and cell cycle signaling pathways between these different growth control methods. Overall, our observations showed that cell cycle arrest by directly targeting CDK4/6 using selective inhibitor compound can be utilized consistently and rapidly to optimize process parameters, such as cell growth, qP, and glycosylation profile in

  11. Weekly cycle of NO2 by GOME measurements: A signature of anthropogenic sources

    NASA Astrophysics Data System (ADS)

    Beirle, S.; Platt, U.; Wenig, M.; Wagner, T.

    2003-07-01

    Nitrogen oxides (NO+NO2=NOx) are important trace gases in the troposphere with impact on human health, atmospheric chemistry and climate. Besides natural sources (lightning, soil emissions) and biomass burning, fossil fuel combustion is estimated to be responsible for about 50% of the total production of NOx. Since human activity in industrialized countries largely follows an artificial seven-day cycle, fossil fuel combustion is expected to be reduced during weekends. This "weekend effect" is well known from local, ground based measurements, but has never been analysed on a global scale before. The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows measurements of NO2 column densities. Applying sophisticated algorithms, vertical column densities (VCD) of tropospheric NO2 can be determined. We demonstrate the statistical analysis of weekly cycles of tropospheric NO2 VCDs for different regions of the world. In the cycles of the industrialized regions and cities in the US, Europe and Japan a clear Sunday minimum of tropospheric NO2 VCD can be seen. Sunday NO2 VCDs are about 25-50% lower than working day levels. Metropolitan areas with other religious and cultural backgrounds (Jerusalem, Mecca) show different weekly patterns corresponding to different days of rest. In China, no weekly pattern can be found. The presence of a weekly cycle in the measured tropospheric NO2 VCD allows the identification of anthropogenic sources. In addition, the fraction of emissions subjected to a weekly cycle (mainly transport, power generation) with respect to a constant background (all kind of natural sources, biomass burning, heavy industry) can be estimated. Furthermore, we estimated the lifetime of tropospheric NO2 by analysing the mean weekly cycle over Germany in detail, obtaining a value of about 12 h.

  12. Response of Cds/CdTe Devices to Te Exposure of Back Contact: Preprint

    SciTech Connect

    Gessert, T. A.; Burst, J. M.; Ma, J.; Wei, S. H.; Kuciauskas, D.; Barnes, T. M.; Duenow, J. N.; Young, M. R.; Rance, W. L.; Li, J. V.; Dippo, P.

    2012-06-01

    Theoretical predictions of thin-film CdS/CdTe photovoltaic (PV) devices have suggested performance may be improved by reducing recombination due to Te-vacancy (VTe) or Te-interstitial (Tei) defects. Although formation of these intrinsic defects is likely influenced by CdTe deposition parameters, it also may be coupled to formation of beneficial cadmium vacancy (VCd) defects. If this is true, reducing potential effects of VTe or Tei may be difficult without also reducing the density of VCd. In contrast, post-deposition processes can sometimes afford a greater degree of defect control. Here we explore a post-deposition process that appears to influence the Te-related defects in polycrystalline CdTe. Specifically, we have exposed the CdTe surface to Te prior to ZnTe:Cu/Ti contact-interface formation with the goal of reducing VTe but without significantly reducing VCd. Initial results show that when this modified contact is used on a CdCl2-treated CdS/CdTe device, significantly poorer device performance results. This suggests two things: First, the amount of free-Te available during contact formation (either from chemical etching or CuTe or ZnTe deposition) may be a more important parameter to device performance than previously appreciated. Second, if processes have been used to reduce the effect of VTe (e.g., oxygen and chlorine additions to the CdTe), adding even a small amount of Te may produce detrimental defects.

  13. Toward semantic-based retrieval of visual information: a model-based approach

    NASA Astrophysics Data System (ADS)

    Park, Youngchoon; Golshani, Forouzan; Panchanathan, Sethuraman

    2002-07-01

    This paper center around the problem of automated visual content classification. To enable classification based image or visual object retrieval, we propose a new image representation scheme called visual context descriptor (VCD) that is a multidimensional vector in which each element represents the frequency of a unique visual property of an image or a region. VCD utilizes the predetermined quality dimensions (i.e., types of features and quantization level) and semantic model templates mined in priori. Not only observed visual cues, but also contextually relevant visual features are proportionally incorporated in VCD. Contextual relevance of a visual cue to a semantic class is determined by using correlation analysis of ground truth samples. Such co-occurrence analysis of visual cues requires transformation of a real-valued visual feature vector (e.g., color histogram, Gabor texture, etc.,) into a discrete event (e.g., terms in text). Good-feature to track, rule of thirds, iterative k-means clustering and TSVQ are involved in transformation of feature vectors into unified symbolic representations called visual terms. Similarity-based visual cue frequency estimation is also proposed and used for ensuring the correctness of model learning and matching since sparseness of sample data causes the unstable results of frequency estimation of visual cues. The proposed method naturally allows integration of heterogeneous visual or temporal or spatial cues in a single classification or matching framework, and can be easily integrated into a semantic knowledge base such as thesaurus, and ontology. Robust semantic visual model template creation and object based image retrieval are demonstrated based on the proposed content description scheme.

  14. Long-term MAX-DOAS network observations of NO2 in Russia and Asia (MADRAS) during the period 2007-2012: instrumentation, elucidation of climatology, and comparisons with OMI satellite observations and global model simulations

    NASA Astrophysics Data System (ADS)

    Kanaya, Y.; Irie, H.; Takashima, H.; Iwabuchi, H.; Akimoto, H.; Sudo, K.; Gu, M.; Chong, J.; Kim, Y. J.; Lee, H.; Li, A.; Si, F.; Xu, J.; Xie, P.-H.; Liu, W.-Q.; Dzhola, A.; Postylyakov, O.; Ivanov, V.; Grechko, E.; Terpugova, S.; Panchenko, M.

    2014-08-01

    We conducted long-term network observations using standardized Multi-Axis Differential optical absorption spectroscopy (MAX-DOAS) instruments in Russia and ASia (MADRAS) from 2007 onwards and made the first synthetic data analysis. At seven locations (Cape Hedo, Fukue and Yokosuka in Japan, Hefei in China, Gwangju in Korea, and Tomsk and Zvenigorod in Russia) with different levels of pollution, we obtained 80 927 retrievals of tropospheric NO2 vertical column density (TropoNO2VCD) and aerosol optical depth (AOD). In the technique, the optimal estimation of the TropoNO2VCD and its profile was performed using aerosol information derived from O4 absorbances simultaneously observed at 460-490 nm. This large data set was used to analyze NO2 climatology systematically, including temporal variations from the seasonal to the diurnal scale. The results were compared with Ozone Monitoring Instrument (OMI) satellite observations and global model simulations. Two NO2 retrievals of OMI satellite data (NASA ver. 2.1 and Dutch OMI NO2 (DOMINO) ver. 2.0) generally showed close correlations with those derived from MAX-DOAS observations, but had low biases of up to ~50%. The bias was distinct when NO2 was abundantly present near the surface and when the AOD was high, suggesting a possibility of incomplete accounting of NO2 near the surface under relatively high aerosol conditions for the satellite observations. Except for constant biases, the satellite observations showed nearly perfect seasonal agreement with MAX-DOAS observations, suggesting that the analysis of seasonal features of the satellite data were robust. Weekend reduction in the TropoNO2VCD found at Yokosuka and Gwangju was absent at Hefei, implying that the major sources had different weekly variation patterns. While the TropoNO2VCD generally decreased during the midday hours, it increased exceptionally at urban/suburban locations (Yokosuka, Gwangju, and Hefei) during winter. A global chemical transport model, MIROC

  15. Suitability of Gray Water for Hydroponic Crop Production Following Biological and Physical Chemical and Biological Subsystems

    NASA Technical Reports Server (NTRS)

    Bubenheim, David L.; Harper, Lynn D.; Wignarajah, Kanapathipillai; Greene, Catherine

    1994-01-01

    The water present in waste streams from a human habitat must be recycled in Controlled Ecological Life Support Systems (CELSS) to limit resupply needs and attain self-sufficiency. Plants play an important role in providing food, regenerating air, and producing purified water via transpiration. However, we have shown that the surfactants present in hygiene waste water have acute toxic effects on plant growth (Bubenheim et al. 1994; Greene et al., 1994). These phytotoxic affects can be mitigated by allowing the microbial population on the root surface to degrade the surfactant, however, a significant suppression (several days) in crop performance is experienced prior to reaching sub-toxic surfactant levels and plant recovery. An effective alternative is to stabilize the microbial population responsible for degradation of the surfactant on an aerobic bioreactor and process the waste water prior to utilization in the hydroponic solution (Wisniewski and Bubenheim, 1993). A sensitive bioassay indicates that the surfactant phytotoxicity is suppressed by more than 90% within 5 hours of introduction of the gray water to the bioreactor; processing for more than 12 hours degrades more than 99% of the phytotoxin. Vapor Compression Distillation (VCD) is a physical / chemical method for water purification which employees sequential distillation steps to separate water from solids and to volatilize contaminants. The solids from the waste water are concentrated in a brine and the pure product water (70 - 90% of the total waste water volume depending on operating conditions) retains non of the phytotoxic effects. Results of the bioassay were used to guide evaluations of the suitability of recovered gray water following biological and VCD processing for hydroponic lettuce production in controlled environments. Lettuce crops were grown for 28 days with 100% of the input water supplied with recovered water from the biological processor or VCD. When compared with the growth of plants

  16. OMI NO2 column densities over North American urban cities: the effect of satellite footprint resolution

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Cheol; Lee, Pius; Judd, Laura; Pan, Li; Lefer, Barry

    2016-03-01

    Nitrogen dioxide vertical column density (NO2 VCD) measurements via satellite are compared with a fine-scale regional chemistry transport model, using a new approach that considers varying satellite footprint sizes. Space-borne NO2 VCD measurement has been used as a proxy for surface nitrogen oxide (NOx) emission, especially for anthropogenic urban emission, so accurate comparison of satellite and modeled NO2 VCD is important in determining the future direction of NOx emission policy. The NASA Ozone Monitoring Instrument (OMI) NO2 VCD measurements, retrieved by the Royal Netherlands Meteorological Institute (KNMI), are compared with a 12 km Community Multi-scale Air Quality (CMAQ) simulation from the National Oceanic and Atmospheric Administration. We found that the OMI footprint-pixel sizes are too coarse to resolve urban NO2 plumes, resulting in a possible underestimation in the urban core and overestimation outside. In order to quantify this effect of resolution geometry, we have made two estimates. First, we constructed pseudo-OMI data using fine-scale outputs of the model simulation. Assuming the fine-scale model output is a true measurement, we then collected real OMI footprint coverages and performed conservative spatial regridding to generate a set of fake OMI pixels out of fine-scale model outputs. When compared to the original data, the pseudo-OMI data clearly showed smoothed signals over urban locations, resulting in roughly 20-30 % underestimation over major cities. Second, we further conducted conservative downscaling of OMI NO2 VCDs using spatial information from the fine-scale model to adjust the spatial distribution, and also applied averaging kernel (AK) information to adjust the vertical structure. Four-way comparisons were conducted between OMI with and without downscaling and CMAQ with and without AK information. Results show that OMI and CMAQ NO2 VCDs show the best agreement when both downscaling and AK methods are applied, with the correlation

  17. Chiral Recognition in Neutral and Ionic Molecular Complexes

    NASA Astrophysics Data System (ADS)

    Sen, Ananya; Bouchet, Aude; Lepere, Valeria; Le Barbu-Debus, Katia; Zehnacker-Rentien, Anne

    2013-06-01

    The behaviour of chiral molecules in the gas phase have been studied. The two pseudoenantiomers of Quinine, have been put intact in the gas phase using laser ablation and characterized using different spectroscopic techniques such as REMPI, LIF, IR-UV double resonance. VCD measurements have been performed in solution. From this comparative study one can conclude that the pseudoenantiomers behave differently both in gas phase and in solution. Ananya Sen, Aude Bouchet, Valeria Lepère, Katia Le Barbu-Debus, D. Scuderi, F. Piuzzi, and A. Zehnacker-Rentien, J. Phys. Chem. A, 2012, 116 (32), pp 8334-8344

  18. Preprototype Vapor Compression Distillation Subsystem development

    NASA Technical Reports Server (NTRS)

    Thompson, C. D.; Ellis, G. S.; Schubert, F. H.

    1981-01-01

    Vapor Compression Distillation (VCD) has evolved as the most promising approach to reclaim potable water from wastewater for future long-term manned space missions. Life Systems, Inc. (LSI), working with NASA, has developed a preprototype Vapor Compression Distillation Subsystem (VCDS) which processes wastewater at 1.4 kg/h. The preprototype unit weighs 143 kg, occupies a volume of 0.47 cu m, and will reclaim 96 percent of the available wastewater. This unit has been tested by LSI and is scheduled for further testing at NASA-JSC. This paper presents the preprototype VCDS design, configuration, performance data, test results and flight system projections.

  19. Investigating the response of East Asian ozone to Chinese emission changes using a linear approach

    NASA Astrophysics Data System (ADS)

    Yamaji, Kazuyo; Uno, Itsushi; Irie, Hitoshi

    2012-08-01

    To illuminate the issue of trans-boundary O3 pollution and regional O3 reduction policies in East Asia, we have investigated the East Asian ozone (O3) response to perturbations caused by Chinese anthropogenic emissions using the Community Multiscale Air Quality (CMAQ) model, a regional chemical transport model. The O3 responses have been examined for the range between -100 and +100% changes from the Chinese emissions level in 2004 in 10% intervals. We have found that springtime and summertime O3 responses both at the source and at the downwind areas can be regarded as linear over the range between -30 and +100% changes from the current emissions level. We therefore suggest that the perturbation between -30 and +100% is sufficiently small to avoid nonlinear chemical influence on O3 formation in a model experiment to investigate East Asian scale O3 source-receptor relationships. On the other hand, the O3 response is strongly nonlinear in April at Hong Kong, where the current NMVOCs/NOx ratio is low and the O3 production regime is easily moved to the NMVOCs sensitive region. The O3 responses to the NOx emission changes have been investigated using surface O3 concentrations at remote Japanese sites and tropospheric NO2 vertical column density (NO2 VCD) over central east China both with observations and with model simulations in springtime during 2003-2009. Analysis of satellite data shows that the observed range of NO2 VCD over central east China in 2003-2009 is the range between -25 and +34% from the 2004 level, which corresponds approximately to an emission variation between -21 and +29%. The O3 concentration in the downwind region during 2003-2009 responds linearly to a change of the NO2 VCD over central east China both in the model and in the observation. The corresponding O3 responses derived from surface observations at remote Japanese sites show linear features consistent with this expectation. The doubling of emissions, i.e., approximately 1.9-fold increase in

  20. Study of the decays D0-->pi{-}e{+}nu{e}, D{0}-->K{-}e{+}nu{e}, D{+}-->pi{0}e{+}nu{e}, and D{+}-->K0e{+}nu{e}.

    PubMed

    Cronin-Hennessy, D; Gao, K Y; Gong, D T; Hietala, J; Kubota, Y; Klein, T; Lang, B W; Poling, R; Scott, A W; Smith, A; Zweber, P; Dobbs, S; Metreveli, Z; Seth, K K; Tomaradze, A; Ernst, J; Severini, H; Dytman, S A; Love, W; Savinov, V; Aquines, O; Li, Z; Lopez, A; Mehrabyan, S; Mendez, H; Ramirez, J; Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shipsey, I P J; Xin, B; Adams, G S; Anderson, M; Cummings, J P; Danko, I; Napolitano, J; He, Q; Insler, J; Muramatsu, H; Park, C S; Thorndike, E H; Yang, F; Coan, T E; Gao, Y S; Liu, F; Artuso, M; Blusk, S; Butt, J; Li, J; Menaa, N; Mountain, R; Nisar, S; Randrianarivony, K; Redjimi, R; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Csorna, S E; Bonvicini, G; Cinabro, D; Dubrovin, M; Lincoln, A; Asner, D M; Edwards, K W; Briere, R A; Brock, I; Chen, J; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E; Rosner, J L; Adam, N E; Alexander, J P; Berkelman, K; Cassel, D G; Duboscq, J E; Ecklund, K M; Ehrlich, R; Fields, L; Gibbons, L; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Onyisi, P U E; Patterson, J R; Peterson, D; Pivarski, J; Riley, D; Ryd, A; Sadoff, A J; Schwarthoff, H; Shi, X; Stroiney, S; Sun, W M; Wilksen, T; Weinberger, M; Athar, S B; Patel, R; Potlia, V; Yelton, J; Rubin, P; Cawlfield, C; Eisenstein, B I; Karliner, I; Kim, D; Lowrey, N; Naik, P; Sedlack, C; Selen, M; White, E J; Wiss, J; Shepherd, M R; Besson, D; Pedlar, T K

    2008-06-27

    By using 1.8x10{6} DDpairs, we have measured B(D{0}-->pi{-}e{+}nu{e})=0.299(11)(9)%, B(D{+}-->pi{0}e{+}nu{e})=0.373(22)(13)%, B(D{0}-->K{-}e{+}nu{e})=3.56(3)(9)%, and B(D{+}-->K{0}e{+}nu{e})=8.53(13)(23)% and have studied the q;{2} dependence of the form factors. By combining our results with recent lattice calculations, we obtain |V{cd}|=0.217(9)(4)(23) and |V{cs}|=1.015(10)(11)(106). PMID:18643653

  1. Water reclamation technology development for future long range missions

    NASA Technical Reports Server (NTRS)

    Flynn, Michael T.; Amo, Karl; Hightower, T. M.; Fisher, John

    1992-01-01

    This paper covers the development of computer simulation models of the Vapor Compression Distillation (VCD) process, the Super Critical Water Oxidation (SCWO) process, and two versions of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) process. These process level models have combined into two Integrated Water Reclamation Systems (IWRS). Results from these integrated models, in conjunction with other data sources, have been used to develop a preliminary comparison of the two systems. Also discussed in this paper is the development of a Vapor Phase Catalytic Ammonia Reduction teststand and the development of a new urine analog for use with the teststand and computer models.

  2. MANTA, a novel plug-based vascular closure device for large bore arteriotomies: technical report.

    PubMed

    van Gils, Lennart; Daemen, Joost; Walters, Greg; Sorzano, Todd; Grintz, Todd; Nardone, Sam; Lenzen, Mattie; De Jaegere, Peter P T; Roubin, Gary; Van Mieghem, Nicolas M

    2016-09-18

    Catheter-based interventions have become a less invasive alternative to conventional surgical techniques for a wide array of cardiovascular diseases but often create large arteriotomies. A completely percutaneous technique is attractive as it may reduce the overall complication rate and procedure time. Currently, large bore arteriotomy closure relies on suture-based techniques. Access-site complications are not uncommon and often seem related to closure device failure. The MANTA VCD is a novel collagen-based closure device that specifically targets arteriotomies between 10 and 22 Fr. This technical report discusses the MANTA design concept, practical instructions for use and preliminary clinical experience. PMID:27639742

  3. Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

    PubMed

    Popik, Oskar; Pasternak-Suder, Monika; Leśniak, Katarzyna; Jawiczuk, Magdalena; Górecki, Marcin; Frelek, Jadwiga; Mlynarski, Jacek

    2014-06-20

    This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  4. The role of computerized modeling and simulation in the development of life support system technologies

    NASA Technical Reports Server (NTRS)

    Modell, Michael; Evanich, Peggy; Chen, Chau-Chyun; Anavi, Selim; Mai, Jeff

    1989-01-01

    Computerized modeling and simulation (CMAS) is a tool that can greatly reduce both the time and cost of technology development. CMAS refers to computer methods for correlating, storing, and retrieving property data for chemical species and for solving the phenomenological equations of physical/chemical processes. Furthermore, process conditions based on properties of materials, mass, and energy balances; equipment sizing based on rate processes; and the governing equations for unit operations can be determined using CMAS. CMAS systems can be used to evaluate an LSS process with minimal requirements for laboratory experimentation. A CMAS model is presented for a vapor compression distillation system(VCD) for reclaiming water from urine.

  5. Stereoselective chemo-enzymatic oxidation routes for (1R,3E,7E,11S,12S)-3,7,18-dolabellatriene

    PubMed Central

    Görner, Christian; Hirte, Max; Huber, Stephanie; Schrepfer, Patrick; Brück, Thomas

    2015-01-01

    The diterpene (1R,3E,7E,11S,12S)-3,7,18-dolabellatriene from the marine brown alga Dilophus spiralis belongs to the dolabellanes natural product family and has antimicrobial activity against multi-drug resistant Staphylococcus aureus. Recently, we generated a CotB2 diterpene synthase mutant (W288G), which instead of its native product cyclooctat-9-en-7-ol, generates (1R,3E,7E,11S,12S)-3,7,18-dolabellatriene. In vivo CotB2 W288G reconstitution in an Escherichia coli based terpene production system, allowed efficient production of this olefinic macrocycle. To diversify the 3,7,18-dolabellatriene bioactivity we evaluated chemical and enzymatic methods for selective oxidation. Epoxidation by acetic peracid, which was formed in situ by a lipase catalyzed reaction of acetic acid with H2O2, provided efficient access to two monooxidized dolabellanes and to a novel di-epoxidated dolabellane species. These compounds could act as synthons en-route to new dolabellanes with diversified bioactivities. Furthermore, we demonstrate the almost quantitative 3,7,18-dolabellatriene conversion into the new, non-natural compound (1R,3E,7E,11S,12S,18R)-dolabella-3,7-diene-20-ol by hydroboration–oxidation with an enantiomeric excess of 94%, for the first time. PMID:26528263

  6. Bio-reducible polycations from ring-opening polymerization as potential gene delivery vehicles.

    PubMed

    Yu, Qing-Ying; Liu, Yan-Hong; Huang, Zheng; Zhang, Ji; Luan, Chao-Ran; Zhang, Qin-Fang; Yu, Xiao-Qi

    2016-07-01

    Synthetic polycations show great potential for the construction of ideal non-viral gene delivery systems. Several cationic polymers were synthesized by the epoxide ring-opening polymerization between diepoxide and various polyamines. Disulfide bonds were introduced to afford the polymers bio-reducibility, while the oxygen-rich structure might enhance the serum tolerance and biocompatibility. The polycations have much lower molecular weights than PEI 25 kDa, but still could well bind and condense DNA into nano-sized particles. DNA could be released from the polyplexes by addition of reductive DTT. Compared to PEI, the polycations have less cytotoxicity possibly due to their lower molecular weights and oxygen-rich structure. More significantly, these materials exhibit excellent serum tolerance than PEI, and up to 6 times higher transfection efficiency than PEI could be obtained in the presence of serum. The transfection mediated by was seldom affected even at a high concentration of serum. Much lower protein adsorption of polycations than PEI was proved by bovine serum albumin adsorption experiments. Flow cytometry also demonstrates their good serum resistance ability.

  7. Dual photochemistry of anthracene-9,10-endoperoxide studied by femtosecond spectroscopy.

    PubMed

    Lauer, Alexandra; Dobryakov, Alexander L; Kovalenko, Sergey A; Fidder, Henk; Heyne, Karsten

    2011-05-21

    The dual photochemistry of anthracene-9,10-endoperoxide (APO) was investigated in a fs UV pump-supercontinuum probe experiment, along with anthracene (AC) and anthraquinone (AQ) for comparison. Excitation of APO at 282 nm leads to 100% product formation by two competing photoreaction channels. Cycloreversion generates with a ∼25% quantum yield (QY) (1)O(2) and AC vibrationally excited in the singlet electronic ground state (hot AC). 1-2% of the AC is generated in the lowest triplet state, but no AC is generated in electronically excited singlet states. Generation and cooling of hot AC are modeled using solution phase and broadened gas-phase AC absorption spectra at various temperatures. Results indicate ultrafast generation of hot AC within 3 ps, much faster than reported before for derivatives of anthracene endoperoxide, and subsequent cooling with an 18 ps time constant. The homolytic O-O cleavage pathway generates a biradical, which converts into electronically excited diepoxide (DE). Our data indicate a 1.5 ps time constant that we tentatively assign to the biradical decay and DE formation. Cooling of DE in this electronically excited state takes place with a ∼21 ps time constant. Excitation of AQ at 266 nm is followed by an ultrafast population of the T(1)(nπ*) triplet state of AQ with a time constant of (160 ± 60) fs.

  8. Carotenoid composition and vitamin A value of an Argentinian squash (Cucurbita moschata).

    PubMed

    González, E; Montenegro, M A; Nazareno, M A; López de Mishima, B A

    2001-12-01

    The carotenoid composition of butternut squash (Cucurbita moschata) cultivated in the province of Santiago del Estero, Argentina, was determined. The main carotenoids isolated were identified as beta-carotene (beta,beta-carotene), alpha-carotene (beta,epsilon-carotene), and lutein (beta,epsilon-carotene-3,3'-diol) and the minor carotenoids, as phytofluene (7,8,11,12,7',8'-hexahydro-psi,psi-carotene), zeta-carotene (7,8,7',8'-tetrahydro-psi,psi-carotene), neurosporene (7,8-dihydro-psi,psi-carotene), violaxanthin (5,6,5',6'- diepoxy-5,6,5',6'-tetrahydro-beta,beta-carotene-3,3'-diol) and neoxanthin (5,6-epoxy-6,7-didehydro-5,6,5',6'-tetrahydro-beta,beta- carotene-3,5,3'-triol). In some samples, 5,6,5',6'-beta-carotene diepoxide, (5,6,5',6'-diepoxy-5,6,5',6'-tetrahydro-beta,beta-carotene) and flavoxanthin (5,8-epoxy-5,8-dihydro-beta,epsilon-carotene-3,3'-diol) were detected. The presence of cis-isomers of beta,beta-carotene was also detected by HPLC. The vitamin A value obtained was 432 micrograms RE/100 g fresh sample, which indicates that this vegetable is an important source of provitamin A.

  9. Mediated glucose enzyme electrodes by cross-linking films of osmium redox complexes and glucose oxidase on electrodes.

    PubMed

    Ó Conghaile, Peter; Kamireddy, Sirisha; MacAodha, Domhnall; Kavanagh, Paul; Leech, Dónal

    2013-04-01

    Here, we report on a novel, versatile approach for the preparation of mediated enzyme electrodes, demonstrated using cross-linked films of glucose oxidase and a range of functionalised osmium complexes on graphite electrodes. Response of enzyme electrodes are optimised by evaluation of glucose response as a function of variation in ratios of [Os(2,2'-bipyridine)2(4-aminomethyl pyridine)Cl](+) redox mediator, polyallylamine support and glucose oxidase enzyme cross-linked using a di-epoxide reagent in films on graphite. Lowering of the redox potential required to mediate glucose oxidation is achieved by synthesis of complexes using (4,4'-dimethyl-2,2'-bipyridine) or (4,4'-dimethoxy-2,2'-bipyridine) as a ligand instead of (2,2'-bipyridine). Enzyme electrodes prepared using the complexes based on dimethoxy- or dimethyl-substituted bipyridines provide glucose oxidation current densities of 30 and 70 μA cm(-2) at 0.2 and 0.35 V applied potential compared to 120 μA cm(-2) at 0.45 V for the initial enzyme electrode, under pseudo-physiological conditions in 5 mM glucose, with stability of signals proving inadequate for long-term operation. Current output and stability may be improved by selection of alternate anchoring and cross-linking methodology, to provide enzyme electrodes capable for application to long-term glucose biosensors and anodes in enzymatic fuel cells.

  10. Oxidation and formation of oxidation products of β-carotene at boiling temperature.

    PubMed

    Zeb, Alam

    2012-04-01

    β-Carotene is one of the most important lipid component extensively used in food industries as source of pro-vitamin A and colorant. During processing and storage β-carotene is oxidized and degraded to various oxidation compounds. Some of these compounds are also the key aroma compounds in certain flowers, vegetables and fruits. The methods for analysis and determination of these oxidized products formed during food boiling or preparation are key to the understanding the chemistry of these compounds. This paper presents a novel analytical method incorporating high performance liquid chromatography with diode array and mass spectrometric detection for the characterization of oxidation, isomerization and oxidation products of β-carotene in toluene at boiling temperature. HPLC and APCI-MS was optimized using oxidized sample and flow injection analysis of the standard β-carotene respectively. β-Carotene was oxidized in the Rancimat at 110°C for 30, 60 and 90 min. The oxidized samples were than analyzed by HPLC system at 450 nm and 350 nm as well as scanning and single ion monitoring mass spectrometry. A total of ten oxidation products and three Z-isomers were reported. Extensive isomerization was observed during treatment at the control accelerated conditions. The oxidation products include five apo-carotenals, three diepoxides, one mono-epoxide and one short chain species. Results show that the method was reproducible, accurate and reliable for the separation and identification of oxidation products of β-carotene.

  11. Double bond stereochemistry influences the susceptibility of short-chain isoprenoids and polyprenols to decomposition by thermo-oxidation.

    PubMed

    Molińska, Ewa; Klimczak, Urszula; Komaszyło, Joanna; Derewiaka, Dorota; Obiedziński, Mieczysław; Kania, Magdalena; Danikiewicz, Witold; Swiezewska, Ewa

    2015-04-01

    Isoprenoid alcohols are common constituents of living cells. They are usually assigned a role in the adaptation of the cell to environmental stimuli, and this process might give rise to their oxidation by reactive oxygen species. Moreover, cellular isoprenoids may also undergo various chemical modifications resulting from the physico-chemical treatment of the tissues, e.g., heating during food processing. Susceptibility of isoprenoid alcohols to heat treatment has not been studied in detail so far. In this study, isoprenoid alcohols differing in the number of isoprene units and geometry of the double bonds, β-citronellol, geraniol, nerol, farnesol, solanesol and Pren-9, were subjected to thermo-oxidation at 80 °C. Thermo-oxidation resulted in the decomposition of the tested short-chain isoprenoids as well as medium-chain polyprenols with simultaneous formation of oxidized derivatives, such as hydroperoxides, monoepoxides, diepoxides and aldehydes, and possible formation of oligomeric derivatives. Oxidation products were monitored by GC-FID, GC-MS, ESI-MS and spectrophotometric methods. Interestingly, nerol, a short-chain isoprenoid with a double bond in the cis (Z) configuration, was more oxidatively stable than its trans (E) isomer, geraniol. However, the opposite effect was observed for medium-chain polyprenols, since Pren-9 (di-trans-poly-cis-prenol) was more susceptible to thermo-oxidation than its all-trans isomer, solanesol. Taken together, these results experimentally confirm that both short- and long-chain polyisoprenoid alcohols are prone to thermo-oxidation.

  12. Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates.

    PubMed

    Boyd, Derek R; Sharma, Narain D; Harrison, John S; Malone, John F; McRoberts, W Colin; Hamilton, John T G; Harper, David B

    2008-04-01

    A series of twelve benzoate esters was metabolised, by species of the Phellinus genus of wood-rotting fungi, to yield the corresponding benzyl alcohol derivatives and eight salicylates. The isolation of a stable oxepine metabolite, from methyl benzoate, allied to evidence of the migration and retention of a carbomethoxy group (the NIH Shift), during enzyme-catalysed ortho-hydroxylation of alkyl benzoates to form salicylates, is consistent with a mechanism involving an initial arene epoxidation step. This mechanism was confirmed by the isolation of a remarkably stable, optically active, substituted benzene oxide metabolite of methyl 2-(trifluoromethyl)benzoate, which slowly converted into the racemic form. The arene oxide was found to undergo a cycloaddition reaction with 4-phenyl-1,2,4-triazoline-3,5-dione to yield a crystalline cycloadduct whose structure and racemic nature was established by X-ray crystallography. The metabolite was also found to undergo some novel benzene oxide reactions, including epoxidation to give an anti-diepoxide, base-catalysed hydrolysis to form a trans-dihydrodiol and acid-catalysed aromatisation to yield a salicylate derivative via the NIH Shift of a carbomethoxy group.

  13. Biologically important eremophilane sesquiterpenes from alaska cedar heartwood essential oil and their semi-synthetic derivatives.

    PubMed

    Khasawneh, Mohammad A; Xiong, Yeping; Peralta-Cruz, Javier; Karchesy, Joe J

    2011-01-01

    The essential oil of Alaska cedar heartwood is known to contain compounds which contribute to the remarkable durability of this species. While previous research has identified several compounds, a complete description of this oil has not been undertaken. In this research a profile of the oil is given in which the major components are identified by GC, isolation and spectroscopic techniques. The major components of the steam distilled essential oil were identified as nootkatin, nootkatone, valencene, nootaktene, carvacrol, methyl carvacrol, nootkatol (2), and eremophil-1(10),11-dien-13-ol (3). The last two compounds were isolated for the first time from Alaska cedar in this research. The absolute stereochemistry at C-2 of nootkatol was shown to have the (S) configuration using the Mosher ester method. Assignment of stereochemistry for valencene-13-ol (3) was established by synthesis from valencene (6). Finally, two related sesquiterpenoids were synthesized from nootkatone and valencene. These sesquiterpenoids were nootkatone-1,10-11,12-diepoxide (5) and valencene-13-aldehyde (4), respectively. PMID:21654582

  14. Conformational study of melectin and antapin antimicrobial peptides in model membrane environments.

    PubMed

    Kocourková, Lucie; Novotná, Pavlína; Čujová, Sabína; Čeřovský, Václav; Urbanová, Marie; Setnička, Vladimír

    2017-01-01

    Antimicrobial peptides have long been considered as promising compounds against drug-resistant pathogens. In this work, we studied the secondary structure of antimicrobial peptides melectin and antapin using electronic (ECD) and vibrational circular dichroism (VCD) spectroscopies that are sensitive to peptide secondary structures. The results from quantitative ECD spectral evaluation by Dichroweb and CDNN program and from the qualitative evaluation of the VCD spectra were compared. The antimicrobial activity of the selected peptides depends on their ability to adopt an amphipathic α-helical conformation on the surface of the bacterial membrane. Hence, solutions of different zwitterionic and negatively charged liposomes and micelles were used to mimic the eukaryotic and bacterial biological membranes. The results show a significant content of α-helical conformation in the solutions of negatively charged liposomes mimicking the bacterial membrane, thus correlating with the antimicrobial activity of the studied peptides. On the other hand in the solutions of zwitterionic liposomes used as models of the eukaryotic membranes, the fraction of α-helical conformation was lower, which corresponds with their moderate hemolytic activity. PMID:27450123

  15. Airborne DOAS observations of tropospheric NO2 using an UltraLight Trike and flux calculation

    NASA Astrophysics Data System (ADS)

    Constantin, Daniel-Eduard; Voiculescu, Mirela; Merlaud, Alexis; Dragomir, Carmelia; Georgescu, Lucian; Hendrick, Francois; Van Roozendael, Michel

    2016-04-01

    In this paper we present airborne DOAS observations of tropospheric NO2 using an Ultralight Trike (ULT) and associated flux calculation. The instrument onboard the ULT was developed for measuring the tropospheric NO2 Vertical Column Density (VCD). Measurements were performed for several days during 2011-2014, in a region SE of Romania, over the cities of Galati (45.43°N, 28.03°E) and Braila (45.26°N, 27.95°E). Measurements of the NO2 column in the same area were performed using car-DOAS observations. The correlation between the tropospheric NO2 VCD from airborne and mobile ground-based DOAS observations was used to validate the airborne observations. A specific AMF for each case was calculated using the radiative transfer model (RTM) UVspec/DISORT. We present also a comparison between SCDstrato derived from DOMINO (Dutch OMI NO2) and the SCDstrato obtained from ground and airborne measurements. Due to the mobility and flexibility of the ULT flights, this aerial platform provides a promising tool for satellite validation, especially for space observations by high resolution sensors such as the future TROPOMI instrument. A key added value of the ULT-DOAS, illustrated in this work, is the capacity to investigate the spatial variability of NO2 inside the horizontal extent of satellite pixels, e.g. above plant exhaust plumes.

  16. Effect of intermixing at CdS/CdTe interface on defect properties

    NASA Astrophysics Data System (ADS)

    Park, Ji-Sang; Yang, Ji-Hui; Barnes, Teresa; Wei, Su-Huai

    2016-07-01

    We investigated the stability and electronic properties of defects in CdTe1-xSx that can be formed at the CdS/CdTe interface. As the anions mix at the interface, the defect properties are significantly affected, especially those defects centered at cation sites like Cd vacancy, VCd, and Te on Cd antisite, TeCd, because the environment surrounding the defect sites can have different configurations. We show that at a given composition, the transition energy levels of VCd and TeCd become close to the valence band maximum when the defect has more S atoms in their local environment, thus improving the device performance. Such beneficial role is also found at the grain boundaries when the Te atom is replaced by S in the Te-Te wrong bonds, reducing the energy of the grain boundary level. On the other hand, the transition levels with respect to the valence band edge of CdTe1-xSx increases with the S concentration as the valence band edge decreases with the S concentration, resulting in the reduced p-type doping efficiency.

  17. Impact of Spectroscopic Line Parameters on Carbon Monoxide Column Density Retrievals from Shortwave Infrared Nadir Observations

    NASA Astrophysics Data System (ADS)

    Schmidt, Denise; Gimeno Garcia, Sebastian; Schreier, Franz; Lichtenberg, Gunter

    2015-06-01

    Among the various input data required for the retrieval of atmospheric state parameters from infrared remote sensing observations molecular spectroscopy line data have a central role, because their quality is critical for the quality of the final product. Here we discuss the impact of the line parameters on vertical column densities (VCD) estimated from short wave infrared nadir observations. Using BIRRA (the Beer InfraRed Retrieval Algorithm) comprising a line-by-line radiative transfer code (forward model) and a separable nonlinear least squares solver for inversion we retrieve carbon monoxide from observations of SCIAMACHY aboard Envisat. Retrievals using recent versions of HITRAN und GEISA have been performed and the results are compared in terms of residual norms, molecular density scaling factors, their corresponding errors, and the final VCD product. The retrievals turn out to be quite similar for all three databases, so a definite recommendation in favor of one of these databases is difficult for the considered spectral range around 2:3 μm . Nevertheless, HITRAN 2012 appears to be advantageous when evaluating the different quality criteria.

  18. Monovision slows juvenile myopia progression unilaterally

    PubMed Central

    Phillips, J R

    2005-01-01

    Aim: To evaluate the acceptability, effectivity, and side effects of a monovision spectacle correction designed to reduce accommodation and myopia progression in schoolchildren. Methods: Dominant eyes of 11 year old children with myopia (−1.00 to −3.00 D mean spherical equivalent) were corrected for distance; fellow eyes were uncorrected or corrected to keep the refractive imbalance ⩽2.00 D. Myopia progression was followed with cycloplegic autorefraction and A-scan ultrasonography measures of vitreous chamber depth (VCD) for up to 30 months. Dynamic retinoscopy was used to assess accommodation while reading. Results: All children accommodated to read with the distance corrected (dominant) eye. Thus, the near corrected eye experienced myopic defocus at all levels of accommodation. Myopia progression in the near corrected eyes was significantly slower than in the distance corrected eyes (inter-eye difference = 0.36 D/year (95% CI: 0.54 to 0.19, p = 0.0015, n = 13); difference in VCD elongation = 0.13 mm/year (95% CI: 0.18 to 0.08, p = 0.0003, n = 13)). After refitting with conventional spectacles, the resultant anisometropia returned to baseline levels after 9–18 months. Conclusions: Monovision is not effective in reducing accommodation in juvenile myopia. However, myopia progression was significantly reduced in the near corrected eye, suggesting that sustained myopic defocus slows axial elongation of the human eye. PMID:16113381

  19. Environmental Control and Life Support Systems Testing Facility at MSFC

    NASA Technical Reports Server (NTRS)

    2001-01-01

    The Marshall Space Flight Center (MSFC) is responsible for designing and building the life support systems that will provide the crew of the International Space Station (ISS) a comfortable environment in which to live and work. Scientists and engineers at the MSFC are working together to provide the ISS with systems that are safe, efficient, and cost-effective. These compact and powerful systems are collectively called the Environmental Control and Life Support Systems, or simply, ECLSS. This photograph shows the Urine Processor Assembly (UPA) which utilizes the Vapor Compression Distillation (VCD) technology. The VCD is used for integrated testing of the entire Water Recovery System (WRS) and development testing of the Urine Processor Assembly. The UPA accepts and processes pretreated crewmember urine to allow it to be processed along with other wastewaters in the Water Processor Assembly (WPA). The WPA removes free gas, organic, and nonorganic constituents before the water goes through a series of multifiltration beds for further purification. Product water quality is monitored primarily through conductivity measurements. Unacceptable water is sent back through the WPA for reprocessing. Clean water is sent to a storage tank.

  20. The γ-Protocadherin-C3 isoform inhibits canonical Wnt signalling by binding to and stabilizing Axin1 at the membrane

    PubMed Central

    Mah, Kar Men; Houston, Douglas W.; Weiner, Joshua A.

    2016-01-01

    The 22 γ-Protocadherin (γ-Pcdh) adhesion molecules encoded by the Pcdhg gene cluster play critical roles in nervous system development, including regulation of dendrite arborisation, neuronal survival, and synaptogenesis. Recently, they have been implicated in suppression of tumour cell growth by inhibition of canonical Wnt signalling, though the mechanisms through which this occurs remain unknown. Here, we show differential regulation of Wnt signalling by individual γ-Pcdhs: The C3 isoform uniquely inhibits the pathway, whilst 13 other isoforms upregulate signalling. Focusing on the C3 isoform, we show that its unique variable cytoplasmic domain (VCD) is the critical one for Wnt pathway inhibition. γ-Pcdh-C3, but not other isoforms, physically interacts with Axin1, a key component of the canonical Wnt pathway. The C3 VCD competes with Dishevelled for binding to the DIX domain of Axin1, which stabilizes Axin1 at the membrane and leads to reduced phosphorylation of Wnt co-receptor Lrp6. Finally, we present evidence that Wnt pathway activity can be modulated up (by γ-Pcdh-A1) or down (by γ-Pcdh-C3) in the cerebral cortex in vivo, using conditional transgenic alleles. Together, these data delineate opposing roles for γ-Pcdh isoforms in regulating Wnt signalling and identify Axin1 as a novel protein interactor of the widely-expressed γ-Pcdh-C3 isoform. PMID:27530555

  1. A variable-collimation display system

    NASA Astrophysics Data System (ADS)

    Batchko, Robert; Robinson, Sam; Schmidt, Jack; Graniela, Benito

    2014-03-01

    Two important human depth cues are accommodation and vergence. Normally, the eyes accommodate and converge or diverge in tandem; changes in viewing distance cause the eyes to simultaneously adjust both focus and orientation. However, ambiguity between accommodation and vergence cues is a well-known limitation in many stereoscopic display technologies. This limitation also arises in state-of-the-art full-flight simulator displays. In current full-flight simulators, the out-the-window (OTW) display (i.e., the front cockpit window display) employs a fixed collimated display technology which allows the pilot and copilot to perceive the OTW training scene without angular errors or distortions; however, accommodation and vergence cues are limited to fixed ranges (e.g., ~ 20 m). While this approach works well for long-range, the ambiguity of depth cues at shorter range hinders the pilot's ability to gauge distances in critical maneuvers such as vertical take-off and landing (VTOL). This is the first in a series of papers on a novel, variable-collimation display (VCD) technology that is being developed under NAVY SBIR Topic N121-041 funding. The proposed VCD will integrate with rotary-wing and vertical take-off and landing simulators and provide accurate accommodation and vergence cues for distances ranging from approximately 3 m outside the chin window to ~ 20 m. A display that offers dynamic accommodation and vergence could improve pilot safety and training, and impact other applications presently limited by lack of these depth cues.

  2. Separating methane emissions from biogenic sources and natural gas by vertical column enhancements of ammonia, ethane, and methane in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Chiu, R.; Volkamer, R. M.; Blumenstock, T.; Hase, F.; Hannigan, J. W.; Kille, N.; Frey, M.; Kumar Sha, M.; Orphal, J.

    2015-12-01

    Methane sources in the Colorado Front Range include biogenic sources from cattle feedlots and natural gas operations. Although numerous studies have measured methane emissions, there remains significant uncertainty regarding the relative contributions of these various methane emission sources. Here we present data from a March 2015 field campaign that deployed two Bruker EM27 Sun Fourier Transform Spectrometers (FTS) and the University of Colorado Solar Occultation Flux (CU-SOF) FTS in Eaton, Colorado; the former were used to measure enhancements in the methane vertical column densities (VCD), while the latter was used to measure ethane and ammonia VCDs. A third EM27 FTS was deployed to a background site in Westminster, Colorado which was far removed from cattle and petroleum operations. Northerly winds make possible the determination of methane VCD column enhancement from Westminster to Eaton. All instruments were compared during several background days at the National Center for Atmospheric Research (NCAR) in Boulder, Colorado. This presentation explores the potential of methane source attribution using ammonia as a tracer for feedlot emissions and ethane as a tracer for petroleum emissions.

  3. Sulfur dioxide (SO2) vertical column density measurements by Pandora spectrometer over the Canadian oil sands

    NASA Astrophysics Data System (ADS)

    Fioletov, Vitali E.; McLinden, Chris A.; Cede, Alexander; Davies, Jonathan; Mihele, Cristian; Netcheva, Stoyka; Li, Shao-Meng; O'Brien, Jason

    2016-07-01

    Vertical column densities (VCDs) of SO2 retrieved by a Pandora spectral sun photometer at Fort McKay, Alberta, Canada, from 2013 to 2015 were analysed. The Fort McKay site is located in the Canadian oil sands region, approximately 20 km north of two major SO2 sources (upgraders), with total emission of about 45 kt yr-1. Elevated SO2 VCD values were frequently recorded by the instrument, with the highest values of about 9 Dobson Units (DU; DU = 2.69 × 1016 molecules cm-2). Comparisons with co-located in situ measurements demonstrated that there was a very good correlation between VCDs and surface concentrations in some cases, while in other cases, elevated VCDs did not correspond to high surface concentrations, suggesting the plume was above the ground. Elevated VCDs and surface concentrations were observed when the wind direction was from south to southeast, i.e. from the direction of the two local SO2 sources. The precision of the SO2 measurements, estimated from parallel measurements by two Pandora instruments at Toronto, is 0.17 DU. The total uncertainty of Pandora SO2 VCD, estimated using measurements when the wind direction was away from the sources, is less than 0.26 DU (1σ). Comparisons with integrated SO2 profiles from concurrent aircraft measurements support these estimates.

  4. Resolution and Determination of the Absolute Configuration of a Twisted Bis-Lactam Analogue of Tröger's Base: A Comparative Spectroscopic and Computational Study.

    PubMed

    Rúnarsson, Ögmundur Vidar; Benkhäuser, Christian; Christensen, Niels Johan; Ruiz, Josep Artacho; Ascic, Erhad; Harmata, Michael; Snieckus, Victor; Rissanen, Kari; Fristrup, Peter; Lützen, Arne; Wärnmark, Kenneth

    2015-08-21

    The first reported twisted bis-lactam, a racemic Tröger's base (TB) analogue (2), was resolved into its enantiomers on a chiral stationary phase HPLC column. The absolute configuration of (+)-2 was determined to be (R,R)-2 by comparing experimental and calculated vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra. The absolute configuration of (-)-2 was determined by comparing experimental and calculated electronic circular dichroism (ECD) spectra. The corresponding theoretical spectra were calculated using the lowest energy conformation of (R,R)-2 and (S,S)-2 at the B3LYP/6-31G(d,p) level of theory. The absolute configuration of (+)-2 was also determined to (R,R)-2 by anomalous X-ray diffraction (AXRD) in a chiral space group P212121 using Cu-irradiation resulting in a very low Flack parameter of -0.06(3), despite the heaviest element being an oxygen atom, thus unambiguously confirming the results from the spectroscopic studies. We conclude that, for the Tröger's base (TB) analogue (2), we may rank the reliability of the individual methods for AC determination as AXRD ≫ VCD > ECD, while the synergy of all three methods provides very strong confidence in the assigned ACs of (+)-(R,R)-2 and (-)-(S,S)-2. PMID:26244379

  5. Helical polyurethane-attapulgite nanocomposite: Preparation, characterization and study of optical activity

    SciTech Connect

    Wang Zhiqiang; Zhou Yuming; Sun Yanqing; Fan Kai; Guo Xingxing; Jiang Xiaolei

    2009-08-15

    Helical polyurethane-attapulgite (BM-ATT) based on R-1,1'-binaphthyl-2',2-diol (R-BINOL) composite was prepared after the surface modification of attapulgite (ATT). BM-ATT was characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HTEM) and vibrational circular dichroism (VCD) spectroscopy. FT-IR and XRD analyses indicate that the helical polyurethane has been successfully grafted onto the surfaces of the modified ATT without destroying the original crystalline structure of ATT. BM-ATT exhibits the rod-like structure by SEM, TEM, and HTEM photographs. BM-ATT displays obvious Cotton effect for some absorbance in VCD spectrum, and its optical activity results from the singlehanded conformation of helical polyurethane. - Graphical Abstract: Helical polyurethane-attapulgite (BM-ATT) based on R-1,1'-binaphthyl-2',2-diol (R-BINOL) nanocomposite was prepared after surface modification of attapulgite (ATT). This rod-like composite is coated by the optically active polyurethane shell on the surfaces.

  6. Performance Assessment of the Exploration Water Recovery System

    NASA Technical Reports Server (NTRS)

    Carter. D. Layne; Tabb, David; Perry, Jay

    2008-01-01

    A new water recovery system architecture designed to fulfill the National Aeronautics and Space Administration s (NASA) Space Exploration Policy has been tested at the Marshall Space Flight Center (MSFC). This water recovery system architecture evolved from the current state-of-the-art system developed for the International Space Station (ISS). Through novel integration of proven technologies for air and water purification, this system promises to elevate existing system optimization. The novel aspect of the system is twofold. First, volatile organic compounds (VOC) are removed from the cabin air via catalytic oxidation in the vapor phase, prior to their absorption into the aqueous phase. Second, vapor compression distillation (VCD) technology processes the condensate and hygiene waste streams in addition to the urine waste stream. Oxidation kinetics dictate that removing VOCs from the vapor phase is more efficient. Treating the various waste streams by VCD reduces the load on the expendable ion exchange and adsorption media which follows, as well as the aqueous-phase catalytic oxidation process further downstream. This paper documents the results of testing this new architecture.

  7. Electronic and optical properties of ceramic Sc2O3 and Y2O3: Compton spectroscopy and first principles calculations

    NASA Astrophysics Data System (ADS)

    Ahuja, Babu Lal; Sharma, Sonu; Heda, Narayan Lal; Tiwari, Shailja; Kumar, Kishor; Meena, Bhoor Singh; Bhatt, Samir

    2016-05-01

    We present the first-ever experimental Compton profiles (CPs) of Sc2O3 and Y2O3 using 740 GBq 137Cs Compton spectrometer. The experimental momentum densities have been compared with the theoretical CPs computed using linear combination of atomic orbitals (LCAO) within density functional theory (DFT). Further, the energy bands, density of states (DOS) and Mulliken's population (MP) data have been calculated using LCAO method with different exchange and correlation approximations. In addition, the energy bands, DOS, valence charge density (VCD), dielectric function, absorption coefficient and refractive index have also been computed using full potential linearized augmented plane wave (FP-LAPW) method with revised functional of Perdew-Becke-Ernzerhof for solids (PBEsol) and modified Becke Johnson (mBJ) approximations. Both the ab-initio calculations predict wide band gaps in Sc2O3 and Y2O3. The band gaps deduced from FP-LAPW (with mBJ) are found to be close to available experimental data. The VCD and MP data show more ionic character of Sc2O3 than Y2O3. The ceramic properties of both the sesquioxides are explained in terms of their electronic and optical properties.

  8. Ab initio quantum mechanical models of peptide helices and their vibrational spectra.

    PubMed

    Bour, Petr; Kubelka, Jan; Keiderling, Timothy A

    2002-10-01

    Structural parameters for standard peptide helices (alpha, 3(10), 3(1) left-handed) were fully ab initio optimized for Ac-(L-Ala)(9)-NHMe and for Ac-(L-Pro)(9)-NHMe (poly-L-proline-PLP I and PLP II-forms), in order to better understand the relative stability and minimum energy geometries of these conformers and the dependence of the ir absorption and vibrational CD (VCD) spectra on detailed variation in these conformations. Only the 3(10)-helical Ala-based conformation was stable in vacuum for this decaamide structure, but both Pro-based conformers minimized successfully. Inclusion of solvent effects, by use of the conductor-like screening solvent model (COSMO), enabled ab initio optimizations [at the DFT/B3LYP/SV(P) level] without any constraints for the alpha- and 3(10)-helical Ala-based peptides as well as the two Pro-based peptides. The geometries obtained compare well with peptide chain torsion angles and hydrogen-bond distances found for these secondary structure types in x-ray structures of peptides and proteins. For the simulation of VCD spectra, force field and intensity response tensors were obtained ab initio for the complete Ala-based peptides in vacuum, but constrained to the COSMO optimized torsional angles, due to limitations of the solvent model. Resultant spectral patterns reproduce well many aspects of the experimental spectra and capture the differences observed for these various helical types.

  9. Stereospecificity in vanadium Schiff base complexes: Formation, crystallization and epimerization processes.

    PubMed

    Krivosudský, Lukáš; Schwendt, Peter; Šimunek, Ján; Gyepes, Róbert

    2015-06-01

    The structures of two stereoisomers of the chiral anion [VO2(N-salicylidene-isoleucinato)](-) possessing three centers of chirality, the vanadium atom (configuration A/C) and the isoleucine moiety (configuration R/S on alpha and beta carbons), are presented. The absolute configuration of all available stereosiomers, CSS, ARR, CSR and ARS, was determined by electronic circular dichroism (ECD), which allows distinguishing between diastereomers, and by vibrational circular dichroism (VCD) capable of differentiating between all four stereoisomers. The comparison of experimental VCD and infrared (IR) spectra with simulated spectra for band assignment revealed the IR spectra of the diastereomers differing significantly in the CH stretching region of the aromatic part in the molecule. Crystallization from binary systems composed of equal ratio of two stereoisomers of isoleucine, unveiled the lower solubility of CSS and ARR stereoisomers, while a longer crystallization time of the CSR and ARS stereoisomers allowed proceeding the vanadium-catalyzed epimerization, leading to the subsequent presence of the CSS and ARR stereoisomers in the product obtained.

  10. Microbiological test results of the environmental control and life support systems vapors compression distillation subsystem recycle tank components following various pretreatment protocols

    NASA Technical Reports Server (NTRS)

    Huff, Tim

    1993-01-01

    Microbiological samples were collected from the recycle tank of the vapor compression distillation (VCD) subsystem of the water recovery test at NASA MSFC following a 68-day run. The recycle tank collects rejected urine brine that was pretreated with a commercially available oxidant (Oxone) and sulfuric acid and pumps it back to the processing component of the VCD. Samples collected included a water sample and two swab samples, one from the particulate filter surface and a second from material floating on the surface of the water. No bacteria were recovered from the water sample. Both swab samples contained a spore-forming bacterium, Bacillus insolitus. A filamentous fungus was isolated from the floating material. Approximately 1 month after the pretreatment chemicals were changed to sodium hypochlorite and sulfuric acid, a swab of the particulate filter was again analyzed for microbial content. One fungus was isolated, and spore-forming bacteria were observed. These results indicate the inability of these pretreatments to inhibit surface attachment. The implications of the presence of these organisms are discussed.

  11. The interplay of aggregation, fibrillization and gelation of an unexpected low molecular weight gelator: glycylalanylglycine in ethanol/water.

    PubMed

    Farrell, Stefanie; DiGuiseppi, David; Alvarez, Nicolas; Schweitzer-Stenner, Reinhard

    2016-07-13

    Hydrogels formed by polypeptides could be much-favored tools for drug delivery because their main ingredients are generally biodegradable. However, the gelation of peptides in aqueous solution generally requires a minimal length of the peptide as well as distinct sequences of hydrophilic and hydrophobic residues. The aggregation of short peptides like tripeptides, which are relatively cheap and offer a high degree of biodegradability, are generally thought to require a high hydrophobicity of their residues. We found that contrary to this expectation cationic glycylalanylglycine in 55 mol% ethanol/45 mol% water forms a gel below a melting temperature of ca. 36 °C. A pure hydrogel state can be obtained after allowing the ethanol component to evaporate. The gel phase consists of crystalline fibrils of several 100 μm, which form a sample-spanning network. Rheological data reveal a soft elastic solid gel. We investigated the kinetics of the various processes that lead to the final gel state of the ternary mixture by a unique combination of UV circular dichroism, infrared, vibrational circular dichroism (VCD) and rheological measurements. A mathematical analysis of our data show that gelation is preceded by the formation of peptide β-sheet like tapes or ribbons, which give rise to a significant enhancement of the amide I' VCD signal, and the subsequent formation of rather thick and long fibrils. The VCD signals indicate that the tapes exhibit a right-handed helicity at temperatures above 16 °C and a left-handed helicity below. The tapes'/ribbons' helicity change occurs at a temperature where the UVCD data reflect a relatively long nucleation process. The kinetics of gel formation probed by the storage and loss moduli are composed of a fast process that follows tape/ribbon/fibril formation and is clearly identifiable in a movie that shows the gelation process and a slow process that causes an additional gel stabilization. The rheological data indicate that left

  12. Interocular symmetry analysis of bilateral eyes.

    PubMed

    Li, Yi; Bao, Fang Jun

    2014-05-01

    The purpose of this study was to evaluate the interocular symmetry of several biometric parameters between both eyes. The symmetry between the right and left eye of 397 subjects in 14 biometric parameters, spherical equivalent of refractive error (SE), Jackson crossed cylinder power of refractive error astigmatism with axes at 90° and 180° (RJ0) and at 45° and 135° (RJ45), best-corrected visual acuity (BCVA), average corneal curvature (CC), Jackson crossed cylinder power of corneal astigmatism (CJ0 and CJ45), corneal asphericity coefficient (Q), intraocular pressure (IOP), central corneal thickness (CCT), axial length (AL), anterior chamber depth (ACD), lens thickness (LT) and vitreous chamber depth (VCD), was assessed by comparative data analysis. Aside from RJ0 (p = 0.00), RJ45 (p = 0.02) and Q (p = 0.00), the overall interocular differences of other biometric parameters between fellow eyes were not significant (p > 0.05). The interocular correlation and Bland-Altman plots showed a good agreement between fellow eyes in 14 biometric parameters. Correlations between interocular differences in SE and that in RJ0 (p = 0.03), CC (p = 0.00), AL (p = 0.00) and VCD (p = 0.00) were statistically significant. There were similar strong linear relationships between refractive error astigmatism vectors and corneal astigmatism vectors in bilateral eyes. There were negative correlations of RJ45 and CJ45 between bilateral eyes. A potentially clinically important interocular symmetry in SE, BCVA, CC, CJ0, CJ45, IOP, CCT, AL, ACD, LT and VCD is found in this research, while the differences of RJ0, RJ45 and Q between left and right eyes seem a bit large. The negative interocular relationships of RJ45 and CJ45 demonstrate moderate mirror symmetry exists among fellow eyes. High interocular symmetry in bilateral eyes may be helpful in intraocular lens power calculation, intraocular pressure evaluation, post-operative visual acuity and refraction

  13. The effect of reading and near-work on the development of myopia in emmetropic boys: a prospective, controlled, three-year follow-up study.

    PubMed

    Hepsen, I F; Evereklioglu, C; Bayramlar, H

    2001-09-01

    This study aimed to investigate the effect of reading and near work on myopic development in emmetropic boys in school age. It involved totally 114 children in two groups. Right eyes of 67 randomly selected students (mean age=12.93) with mean 6 h of reading and near work (Group 1) were compared with the right eyes of 47 apprentices (mean age=12.96) working as skilled laborers (Group 2). Cycloplegic refraction, keratometric readings and biometric measurements including anterior chamber depth (ACD), lens thickness (LT), vitreous chamber depth (VCD) and axial length (AL) were performed for 3 years at 18 month intervals. Two analyses were conducted: (1) for subjects in both groups with baseline refractive error from +0.50 to -0.50 D; (2) for all subjects in both groups with baseline refractive error from +1.00 to -1.00 D. For subjects with baseline refractive error of +/-0.50 D, myopic shift was present in 20 of 41 (48.8%) in group 1 and in seven of 37 (18.9%) in group 2 at the end of the study. The magnitude of the myopic shift was 0.56 and 0.07 D in group 1 and 2, respectively. For subjects with a baseline refractive error of +/-1.00 D, myopic progression was present in 40 of 67 (59.7%) in group 1 and in 10 of 47 (21.3%) in group 2 at the last readings. In this larger refractive range, the magnitude of the myopic shift was 0.61 and 0.12 D in group 1 and 2, respectively. The mean ACD, VCD and AL were significantly higher in the last readings after 36 months than in the first readings (for each, P=0.0001) in group 1. There was no statistically significant difference between two measurements of these parameters in group 2. The final keratometric dioptric readings were lower than the first values (for each, P=0.0001) in both groups at the end of the study. This prospective and controlled study suggested that reading and near work, important environmental factors, might cause refractive myopic shifts in emmetropic students. The myopic shift was primarily related to

  14. Alkyltransferase-mediated toxicity of bis-electrophiles in mammalian cells

    PubMed Central

    Kalapila, Aley G.; Pegg, Anthony E.

    2009-01-01

    The primary function of O6-alkylguanine-DNA alkyltransferase (AGT) is to maintain genomic integrity in the face of damage by both endogenous and exogenous alkylating agents. However, paradoxically, bacterial and mammalian AGTs have been shown to increase cytotoxicity and mutagenicity of dihaloalkanes and other bis-electrophiles when expressed in bacterial cells. We have extended these studies to mammalian cells using CHO cells that lack AGT expression and CHO cells stably transfected with a plasmid that expresses human AGT. The cytotoxicity of 1,2-dibromoethane, dibromomethane and epibromohydrin was significantly increased by the presence of AGT but cytotoxicity of butadiene diepoxide was not affected. Mutations caused by these agents were assessed using hypoxanthine-guanine phosphoribosyltransferase (HPRT) as a reporter gene. There was a small (c. 2–3-fold) but statistically significant AGT-mediated increase in mutations caused by 1,2-dibromoethane, dibromomethane and epibromohydrin. Analysis of the mutation spectrum induced by 1,2-dibromoethane showed that the presence of AGT also altered the types of mutations with an increase in total base substitution mutants due to a rise in transversions at both G:C and A:T sites. AGT expression also led to mutations arising from the transcribed strand, which were not seen in cells lacking AGT. Although the frequency of deletion mutations was decreased by AGT expression, the formation of large deletions (≥3 exons) was increased. This work demonstrates that interaction of AGT with some bis-electrophiles can cause mutagenicity and diminished cell survival in mammalian cells. It is consistent with the hypothesis that DNA-AGT cross-links, which have been characterized in experiments with purified AGT protein and such bis-electrophiles, can be formed in mammalian cells. PMID:19941875

  15. Effect of O6-Alkylguanine-DNA Alkyltransferase on Genotoxicity of Epihalohydrins

    PubMed Central

    Kalapila, Aley G.; Loktionova, Natalia A.; Pegg, Anthony E.

    2010-01-01

    The effect of O6-alkylguanine-DNA alkyltransferase (AGT) on the toxicity and mutagenicity of epihalohydrins was studied. AGT is a DNA repair protein that protects cells from agents that produce genotoxic O6-alkylguanine lesions by transferring the alkyl group to an internal cysteine residue (Cys145 in human AGT) in a single-step. This cysteine acceptor site is highly reactive and epihalohydrins reacted readily with AGT at this site with a halide order of reactivity of Br > Cl > F. AGT expression in bacterial cells caused a very large increase in the mutagenicity and cytotoxicity of epibromohydrin. The mutations were almost all G:C to A:T transitions. Epichlorohydrin also augmented AGT-mediated mutagenesis but to a lesser extent than epibromohydrin. In vitro experiments showed that AGT was covalently cross-linked to DNA in the presence of epibromohydrin and that this conjugation occurred predominantly at Cys145, and to a smaller extent at Cys150, a less reactive residue also located within the active site pocket. Two pathways yielding the AGT-DNA adduct were found to occur. The predominant mechanism results in an AGT-epihalohydrin intermediate, which, facilitated by the DNA binding properties of AGT, then reacts covalently with DNA. The second pathway involves an initial reactive DNA-epihalohydrin intermediate that subsequently reacts with AGT. Our results show that the paradoxical AGT-mediated increase in genotoxicity which has previously been shown to occur with dihaloalkanes, butadiene diepoxide and nitrogen mustards, also occurs with epihalohydrins and is likely to contribute to their toxicity and mutagenicity. PMID:19472322

  16. Kinetics of naphthalene metabolism in target and non-target tissues of rodents and in nasal and airway microsomes from the Rhesus monkey

    SciTech Connect

    Buckpitt, Alan; Morin, Dexter; Murphy, Shannon; Edwards, Patricia; Van Winkle, Laura

    2013-07-15

    Naphthalene produces species and cell selective injury to respiratory tract epithelial cells of rodents. In these studies we determined the apparent K{sub m}, V{sub max}, and catalytic efficiency (V{sub max}/K{sub m}) for naphthalene metabolism in microsomal preparations from subcompartments of the respiratory tract of rodents and non-human primates. In tissues with high substrate turnover, major metabolites were derived directly from naphthalene oxide with smaller amounts from conjugates of diol epoxide, diepoxide, and 1,2- and 1,4-naphthoquinones. In some tissues, different enzymes with dissimilar K{sub m} and V{sub max} appeared to metabolize naphthalene. The rank order of V{sub max} (rat olfactory epithelium > mouse olfactory epithelium > murine airways ≫ rat airways) correlated well with tissue susceptibility to naphthalene. The V{sub max} in monkey alveolar subcompartment was 2% that in rat nasal olfactory epithelium. Rates of metabolism in nasal compartments of the monkey were low. The catalytic efficiencies of microsomes from known susceptible tissues/subcompartments are 10 and 250 fold higher than in rat airway and monkey alveolar subcompartments, respectively. Although the strong correlations between catalytic efficiencies and tissue susceptibility suggest that non-human primate tissues are unlikely to generate metabolites at a rate sufficient to produce cellular injury, other studies showing high levels of formation of protein adducts support the need for additional studies. - Highlights: • Naphthalene is metabolized with high catalytic efficiency in susceptible tissue. • Naphthalene is metabolized at low catalytic efficiency in non-susceptible tissue. • Respiratory tissues of the non human primate metabolize naphthalene slowly.

  17. A novel method to directionally stabilize enzymes together with redox mediators by electrodeposition.

    PubMed

    Shi, Wentao; Lin, Nansen; Song, Yilin; Liu, Chunxiu; Zhou, Shuai; Cai, Xinxia

    2014-01-15

    This paper depicts a novel method to directionally stabilize enzymes together with redox mediators by electrodeposition. Chitosan was used as a stabilizing matrix. By electrochemical removal of local H(+), chitosan close to working electrode became locally insoluble, and enzymes and redox mediators in chitosan were stabilized. The microelectrode on home-made microelectrode array (MEA) served as the working electrode. Three model enzymes--horseradish peroxidase (HRP), glucose oxidase (GOD), and glutamate oxidase (GlOD)--were used to fabricate different biosensors, and the redox mediator model was a poly(vinylpyridine) complex of Os(bpy)2Cl and a diepoxide (PVP-Os). Biosensors fabricated by the method exhibited very high performance. For HRP biosensor fabricated by this method, the sensitivity was 5.274 nA μM(-1) mm(-2), with linear detection range (LDR) of 2-220 μM and limit of detection (LOD) of 1 μM (S/N=3); for GOD biosensor, the sensitivity was 2.65 nA μM(-1) mm(-2), with LDR of 4-500 μM and LOD of 2 μM (S/N=3); for GlOD biosensor, the sensitivity was 0.33 nA μM(-1)mm(-2), with LDR of 4-500 μM and LOD of 2 μM (S/N=3). Since this method is very simple and especially suitable for directionally introducing enzymes and redox mediators onto microelectrode without contaminating other sites in the same microenvironment, it could be used for fabricating in vivo or in vitro 2nd generation biosensors in μm-scale, especially in neuroscience.

  18. Carrier Density and Compensation in Semiconductors with Multi Dopants and Multi Transition Energy Levels: The Case of Cu Impurity in CdTe: Preprint

    SciTech Connect

    Wei, S. H.; Ma, J.; Gessert, T. A.; Chin, K. K.

    2011-07-01

    Doping is one of the most important issues in semiconductor physics. The charge carrier generated by doping can profoundly change the properties of semiconductors and their performance in optoelectronic device applications, such as solar cells. Using detailed balance theory and first-principles calculated defect formation energies and transition energy levels, we derive general formulae to calculate carrier density for semiconductors with multi dopants and multi transition energy levels. As an example, we studied CdTe doped with Cu, in which VCd, CuCd, and Cui are the dominant defects/impurities. We show that in this system, when Cu concentration increases, the doping properties of the system can change from a poor p-type, to a poorer p-type, to a better p-type, and then to a poor p-type again, in good agreement with experimental observation of CdTe-based solar cells.

  19. A facile method to determine the absolute structure of achiral molecules: supramolecular-tilt structures.

    PubMed

    Tejedor, Rosa María; Uriel, Santiago; Graus, Sara; Sierra, Teresa; Serrano, José Luis; Claramunt, Rosa M; López, Concepción; Pérez-Torralba, Marta; Alkorta, Ibon; Elguero, José

    2013-05-01

    Achiral compounds 4-methoxy-4-(p-methoxyphenyl)cyclohexanoneethylene ketal (2), 4-hydroxy-4-(p-methoxy phenyl)cyclohexanoneethylene ketal (3), and 3,5-dimethyl-4-nitropyrazole (4) crystallized in chiral structures and the samples showed an enantiomeric excess. We have determined the absolute structures of these compounds by using X-ray diffraction with copper radiation at low temperatures. Moreover, we have also established the prevalent absolute structures in these samples, by comparing their calculated and solid-state vibrational circular dichroism (VCD) spectra. The consistency of this method was confirmed by using (R,R)-2,8-diiodo-4,10-dimethyl-6 H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine, Tröger's base, (R,R)-1, as a chiral compound of known absolute configuration.

  20. NO2 evolution at global level using the space instruments SCIAMACHY, OMI and GOME-2

    NASA Astrophysics Data System (ADS)

    Rosu, Adrian; Constantin, Daniel-Eduard; Bocaneala, Corina; Voiculescu, Mirela; Puiu Georgescu, Lucian

    2016-04-01

    The main objective of this study is to evaluate the amount of NO2 at global level above twenty five worldwide urban agglomerations or station during 2002-2015. Tropospheric NO2 Vertical Column Density (VCD) are derived from various satellite UV-Vis instruments: SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric ChartographY) onboard Envisat, OMI (Ozone Monitoring Instrument) onboard AURA and GOME-2 (Global Ozone Monitoring Experiment Measurements-2) onboard Metop-A& B. Possible dependence of the evolution of the density of NO2 molecules above the major cities on demographic, economic, industry characteristics are investigated. Causes for various trends of the NO2 column, depending on geographical characteristics, altitude, are also analysed.

  1. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    PubMed Central

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-01-01

    The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis. PMID:25960309

  2. Diterpenes from the endangered goldenrod Solidago shortii.

    PubMed

    Williams, Russell B; Du, Lin; Norman, Vanessa L; Goering, Matt G; O'Neil-Johnson, Mark; Woodbury, Scott; Albrecht, Matthew A; Powell, Douglas R; Cichewicz, Robert H; Eldridge, Gary R; Starks, Courtney M

    2014-06-27

    Species extinction is tantamount to loss of chemical diversity, and so it is important to seize all opportunities to study species on the brink of extinction. Such studies are often hampered by the limited material available, but that obstacle is surmountable through collaboration with botanical gardens and advances in instrumentation. The goldenrod Solidago shortii is one example of an endangered species native to the United States. From S. shortii, one known diterpene (1), two new diterpenes (2 and 3), and three new hydrolysis products (4-6) are described. This work was made possible through collaboration with the Missouri Botanical Garden and with the use of highly sensitive microcryoprobe NMR technology for structure elucidation and VCD spectroscopy for the determination of absolute configuration.

  3. Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study.

    PubMed

    Sen, Ananya; Bouchet, Aude; Lepère, Valeria; Le Barbu-Debus, Katia; Scuderi, D; Piuzzi, F; Zehnacker-Rentien, A

    2012-08-16

    Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.

  4. Deep level defect luminescence in cadmium selenide nano-crystals films

    NASA Astrophysics Data System (ADS)

    Babentsov, V.; Riegler, J.; Schneider, J.; Ehlert, O.; Nann, T.; Fiederle, M.

    2005-07-01

    Undoped CdSe monocrystals and CdSe nano-crystals films have been studied at various temperatures by continuous wave (cw) photoluminescence. We report on a characteristic deep level emission, which is consistently observed in the wurtzite bulk- and nanocrystalline forms of CdSe. Two broad luminescence bands, which are separated from the excitonic emission by 0.5 and 0.7 eV occur in CdSe, prepared by quite different techniques. These bands experience, similar to the excitonic emission, a spectral shift to high energy enforced by the quantum confinement in nano-CdSe. The defects responsible for this luminescence are probably two different VCd- VSe divacancies: one is oriented along the hexagonal c-axis, the other is oriented along the basal Cd-Se bond directions.

  5. Reduced energy consumption evaporator for use in desalting impaired waters. Technical completion report (Final)

    SciTech Connect

    Tleimat, B.W.; Tleimat, M.C.

    1995-06-01

    The basic objective of this program is to demonstrate significant savings in energy consumption by the use of the wiped film rotating disk (WFRD) evaporator in a five-effect vapor compression distillation (MEVCD) system to recover the maximum amount of water from agricultural drainage water and other impaired waters. Tests were conducted using a 10,000 ppm aqueous solution of sodium sulfate and sodium chloride to simulate the composition of agricultural drainage water in the San Joaquin Valley, California. The feed was concentrated by a factor ranging from 15 to 20 resulting in a blowdown salinity of 150,000 to 200,000 ppm. The results showed the presence of dissolved salts has significant influence on energy consumption by the compressor of a commercial 60,000 gal/day VCD unit tested at Los Banos, California.

  6. On the opportunity of an increased degree of stability of parameters and characteristics of IR photoreceivers based on Mo/CdS1-xSex

    NASA Astrophysics Data System (ADS)

    Abdinov, A. S.; Mamedov, H. M.; Hasanov, H. A.

    2005-06-01

    The processes of photochemical reorganization of deep levels of the photoactive centers in films CdS1-xSex (0 <= x <= 0.8) prepared onto molybdenum substrates by the method of electrochemical deposition were investigated. It is established that thermal annealing of investigated films in air at Ta=380 -400°C for τa=7-8 min leads to occurrence of new longwavelength maximum in the photosensitivity spectrum at λ=0.95-1.15 μm (depending on the selenium content) which is due to oxygen-containing photoactive centers forming at disintegration of (VCd-Cdi)+ pairs. The mechanism of formation and disintegration of donor-acceptor pairs have been proposed and basic parameters of complex centers formed at thermal annealing were determined by the method of photocapacitance and photoconductivity spectroscopy.

  7. Simulation of Vibrational Spectra of Large Molecules by Arbitrary Time Propagation.

    PubMed

    Kubelka, Jan; Bouř, Petr

    2009-01-13

    Modern ab initio and multiscale methods enable the simulation of vibrational properties of very large molecules. Within the harmonic approximation, the traditional generation of the spectra based on the force field diagonalization can become inefficient due to the excessive demands on computer time and memory. The present study proposes to avoid completely the matrix diagonalization with a direct generation of the spectral shapes. For infrared absorption (IR) and vibrational circular dichroism (VCD) electric and magnetic dipole moments are propagated in a fictitious time and spectral intensities are obtained by Fourier transformation. The algorithm scales quasi-linearly, and for model polypeptide molecules the method was found numerically stable and faithfully reproduced exact transition frequencies and relative intensities.

  8. Study of the semileptonic charm decays D(0)-->pi(-)l(+)nu and D(0)-->K(-)l(+)nu.

    PubMed

    Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shibata, E I; Shipsey, I P J; Adams, G S; Chasse, M; Cummings, J P; Danko, I; Napolitano, J; Cronin-Hennessy, D; Park, C S; Park, W; Thayer, J B; Thorndike, E H; Coan, T E; Gao, Y S; Liu, F; Stroynowski, R; Artuso, M; Boulahouache, C; Blusk, S; Butt, J; Dambasuren, E; Dorjkhaidav, O; Menaa, N; Mountain, R; Muramatsu, H; Nandakumar, R; Redjimi, R; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Mahmood, A H; Csorna, S E; Bonvicini, G; Cinabro, D; Dubrovin, M; Bornheim, A; Lipeles, E; Pappas, S P; Weinstein, A J; Briere, R A; Chen, G P; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E; Adam, N E; Alexander, J P; Berkelman, K; Cassel, D G; Duboscq, J E; Ecklund, K M; Ehrlich, R; Fields, L; Galik, R S; Gibbons, L; Gittelman, B; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Hsu, L; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Meyer, T O; Onyisi, P U E; Patterson, J R; Pedlar, T K; Peterson, D; Pivarski, J; Riley, D; Rosner, J L; Ryd, A; Sadoff, A J; Schwarthoff, H; Shepherd, M R; Sun, W M; Thayer, J G; Urner, D; Wilksen, T; Weinberger, M; Athar, S B; Avery, P; Breva-Newell, L; Patel, R; Potlia, V; Stoeck, H; Yelton, J; Rubin, P; Cawlfield, C; Eisenstein, B I; Gollin, G D; Karliner, I; Kim, D; Lowrey, N; Naik, P; Sedlack, C; Selen, M; Thaler, J J; Williams, J; Wiss, J; Edwards, K W; Besson, D; Gao, K Y; Gong, D T; Kubota, Y; Li, S Z; Poling, R; Scott, A W; Smith, A; Stepaniak, C J; Urheim, J; Metreveli, Z; Seth, K K; Tomaradze, A; Zweber, P; Ernst, J; Arms, K; Gan, K K; Severini, H; Skubic, P; Asner, D M; Dytman, S A; Mehrabyan, S; Mueller, J A; Savinov, V; Li, Z; Lopez, A; Mendez, H; Ramirez, J

    2005-01-14

    We investigate the decays D(0)-->pi(-)l(+)nu and D(0)-->K(-)l(+)nu, where l is e or mu, using approximately 7 fb(-1) of data collected with the CLEO III detector. We find R(0) identical with B(D(0)-->pi(-)e(+)nu)/B(D(0)-->K(-)e(+)nu)=0.082+/-0.006+/-0.005. Fits to the kinematic distributions of the data provide parameters describing the form factor of each mode. Combining the form factor results and R(0) gives |f(pi)(+)(0)|(2)|V(cd)|(2)/|f(K)(+)(0)|(2)|V(cs)|(2)=0.038(+0.006+0.005)(-0.007-0.003). PMID:15698066

  9. NO2 and HCHO variability in Mexico City from MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Grutter, M.; Friedrich, M. M.; Rivera, C. I.; Arellano, E. J.; Stremme, W.

    2015-12-01

    Atmospheric studies in large cities are of great relevance since pollution affects air quality and human health. A network of Multi Axis Differential Optical Absorption Spectrometers (MAX-DOAS) has been established in strategic sites within the Mexico City metropolitan area. Four instruments are now in operation with the aim to study the variability and spatial distribution of key pollutants, providing results of O4, NO2 and HCHO slant column densities (SCD). A numerical code has been written to retrieve gas profiles of NO2 and HCHO using radiative transfer simulations. We present the first results of the variability of these trace gases which will bring new insight in the current knowledge of transport patterns, emissions as well as frequency and origin of extraordinary events. Results of the vertical column densities (VCD) valiability of NO2 and HCHO in Mexico City are presented. These studies are useful to validate current and future satellite observatopns such as OMI, TROPOMI and TEMPO.

  10. Modification of band gap in surface layer in Cd 1-xZn xTe by YAG:Nd +3 laser radiation

    NASA Astrophysics Data System (ADS)

    Medvid, Artur; Fedorenko, Leonid L.; Korbutjak, Dmytro V.; Kryluk, Sergiy G.; Yusupov, Mikola M.; Mychko, Aleksandr

    2007-02-01

    A mechanism of formation of graded band-gap based on Thermogradient Effect (TGE) is proposed in Cd 1-xZn xTe at irradiation by second harmonic of a Q-switched YAG:Nd laser. According to the effect, the interstitial atoms of Cd (Cd i) in Cd 1-xZn xTe move along the temperature gradient while the Cd vacancies (V Cd) and Zn atoms - in the opposite direction, into the bulk of the semiconductor where temperature is lower. Photoluminescence (PL) spectra studied at 5 K show that concentration of Zn atoms increases due to aggregation of VCd with Zn after laser irradiation. Formation of a graded band-gap in Cd 1-xZn xTe crystal at irradiation by second harmonica of YAG:Nd laser by is shown to be possible.

  11. Quark Mixing and Preon Model

    NASA Astrophysics Data System (ADS)

    Senju, H.

    1991-07-01

    Inspired by unique features of the preon-subpreon model, we propose a new scheme for quark mixing. In our scheme, the mass relations m_{d} << m_{s} << m_{b} and m_{u} << m_{c} << m_{t} are naturally understood. The resultant CKM matrix has very nice properties. The fact that |V_{us}| and |V_{cd}| are remarkably large compared with other off-diagonal elements is naturally understood. |V_{cb}| =~ |V_{ts}| is predicted and their small values are explained. |V_{ub}| and |V_{td}| are predicted to be much smaller than |V_{cb}|. The parametrization invariant measure of CP violation, J, is predicted to be |V_{ud}| |V_{ub}| |V_{td}| sin phi. The mass relations and mixings of q', q'', l_{s} and leptons are also discussed.

  12. [Retrieval of tropospheric NO2 by multi axis differential optical absorption spectroscopy].

    PubMed

    Xu, Jin; Xie, Pin-hua; Si, Fu-qi; Dou, Ke; Li, Ang; Liu, Yu; Liu, Wen-qing

    2010-09-01

    A method of retrieving NO2 in troposphere based on multi axis differential optical absorption spectroscopy (MAX-DOAS) was introduced. The differential slant column density (dSCD) of NO2 was evaluated by differential optical absorption spectroscopy (DOAS), removing the Fraunhofer structure and Ring effect. Combining the results of different observing directions, the tropospheric NO2 differential slant column density (deltaSCD) was evaluated, and the air mass factor (AMF) was calculated with the radiative transfer model SCIATRAN and the tropospheric NO2 vertical column density (VCD) was retrieved. To ensure the accuracy of the results, it was compared with the results of long path differential optical absorption spectroscopy (LP-DOAS), a good accordance was shown with the correlation coefficients of 0.94027 and 0.96924. PMID:21105419

  13. Development Status of the International Space Station Urine Processor Assembly

    NASA Technical Reports Server (NTRS)

    Holder, Donald W.; Hutchens, Cindy F.

    2003-01-01

    NASA, Marshall Space Flight Center (MSFC) is developing a Urine Processor Assembly (UPA) for the International Space Station (ISS). The UPA uses Vapor Compression Distillation (VCD) technology to reclaim water from pre-treated urine. This water is further processed by the Water Processor Assembly (WPA) to potable quality standards for use on the ISS. NASA has developed this technology over the last 25-30 years. Over this history, many technical issues were solved with thousands of hours of ground testing that demonstrate the ability of the UPA technology to reclaim water from urine. In recent years, NASA MSFC has been responsible for taking the UPA technology to "flight design" maturity. This paper will give a brief overview of the UPA design and a status of the major design and development efforts completed recently to mature the UPA to a flight level.

  14. Implementation and validation of a multi-purpose virtual spectrometer for large systems in complex environments.

    PubMed

    Barone, Vincenzo; Baiardi, Alberto; Biczysko, Malgorzata; Bloino, Julien; Cappelli, Chiara; Lipparini, Filippo

    2012-09-28

    Despite impressive advances of computational spectroscopy, a robust and user-friendly multi-frequency virtual spectrometer is not yet available. This contribution summarises ongoing efforts in our research group toward the implementation and validation of such a tool with special reference to the building blocks of biomolecules in their natural environment. Our integrated computational tool allows the computation of several kinds of spectra, including vibrational (e.g. IR, VCD), electronic (e.g. absorption, emission, ECD) as well as magnetic resonance (e.g. ESR, NMR) for both closed- and open-shell systems in vacuo and in condensed phases, and includes facilities for drawing, comparing, and modifying all the computed spectra. A number of test cases involving a combination of different spectroscopic ranges will be discussed in order to point out strengths, limitations, and ongoing developments of our research plan.

  15. Detailed Modeling of Distillation Technologies for Closed-Loop Water Recovery Systems

    NASA Technical Reports Server (NTRS)

    Allada, Rama Kumar; Lange, Kevin E.; Anderson, Molly S.

    2011-01-01

    Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA?s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents efforts to develop chemical process simulations for three technologies: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system and the Wiped-Film Rotating Disk (WFRD) using the Aspen Custom Modeler and Aspen Plus process simulation tools. The paper discusses system design, modeling details, and modeling results for each technology and presents some comparisons between the model results and recent test data. Following these initial comparisons, some general conclusions and forward work are discussed.

  16. Diterpenes from the endangered goldenrod Solidago shortii.

    PubMed

    Williams, Russell B; Du, Lin; Norman, Vanessa L; Goering, Matt G; O'Neil-Johnson, Mark; Woodbury, Scott; Albrecht, Matthew A; Powell, Douglas R; Cichewicz, Robert H; Eldridge, Gary R; Starks, Courtney M

    2014-06-27

    Species extinction is tantamount to loss of chemical diversity, and so it is important to seize all opportunities to study species on the brink of extinction. Such studies are often hampered by the limited material available, but that obstacle is surmountable through collaboration with botanical gardens and advances in instrumentation. The goldenrod Solidago shortii is one example of an endangered species native to the United States. From S. shortii, one known diterpene (1), two new diterpenes (2 and 3), and three new hydrolysis products (4-6) are described. This work was made possible through collaboration with the Missouri Botanical Garden and with the use of highly sensitive microcryoprobe NMR technology for structure elucidation and VCD spectroscopy for the determination of absolute configuration. PMID:24922615

  17. Chiroptical properties of streptorubin B: the synergy between theory and experiment.

    PubMed

    Andrade, Marta S; Silva, Vanessa S; Lourenço, Ana M; Lobo, Ana M; Rzepa, Henry S

    2015-10-01

    Analysis of the calculated and measured optical rotation (OR) together with other calculated chiroptical properties such as electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) of the prodigiosin alkaloid streptorubin B shows that these are dominated by the pseudoenantiomeric atropisomers anti-(S)-streptorubin B (1A) and syn-(S)-streptorubin (1B). Atropisomerism is a dynamic phenomenon with a potentially nonequilibrium population of isomers, and accordingly the measured chiroptical responses may vary with time, concentration, temperature, and the anion of the salts used. Streptorubin also has the potential to form stacked homodimers for which the optical rotations measured at 589 nm can vary greatly due to the presence of ECD-active electronic transitions in this region.

  18. Revisiting Verhulst and Monod models: analysis of batch and fed-batch cultures.

    PubMed

    Shirsat, Nishikant; Mohd, Avesh; Whelan, Jessica; English, Niall J; Glennon, Brian; Al-Rubeai, Mohamed

    2015-05-01

    The paper re-evaluates Verhulst and Monod models. It has been claimed that standard logistic equation cannot describe the decline phase of mammalian cells in batch and fed-batch cultures and in some cases it fails to fit somatic growth data. In the present work Verhulst, population-based mechanistic growth model was revisited to describe successfully viable cell density (VCD) in exponential and decline phases of batch and fed-batch cultures of three different CHO cell lines. Verhulst model constants, K, carrying capacity (VCD/ml or μg/ml) and r, intrinsic growth factor (h(-1)) have physical meaning and they are of biological significance. These two parameters together define the course of growth and productivity and therefore, they are valuable in optimisation of culture media, developing feeding strategies and selection of cell lines for productivity. The Verhulst growth model approach was extended to develop productivity models for batch and fed-batch cultures. All Verhulst models were validated against blind data (R(2) > 0.95). Critical examination of theoretical approaches concluded that Monod parameters have no physical meaning. Monod-hybrid (pseudo-mechanistic) batch models were validated against specific growth rates of respective bolus and continuous fed-batch cultures (R(2) ≈ 0.90). The reduced form of Monod-hybrid model CL/(KL + CL) describes specific growth rate during metabolic shift (R(2) ≈ 0.95). Verhulst substrate-based growth models compared favourably with Monod-hybrid models. Thus, experimental evidence implies that the constants in the Monod-hybrid model may not have physical meaning but they behave similarly to the biological constants in Michaelis-Menten enzyme kinetics, the basis of the Monod growth model.

  19. Effect of D-amino acids at Asp{sup 23} and Ser{sup 26} residues on the conformational preference of A{beta}{sub 20-29} peptides

    SciTech Connect

    Shanmugam, Ganesh; Polavarapu, Prasad L. . E-mail: Prasad.L.Polavarapu@Vanderbilt.edu; Hallgas, Balazs; Majer, Zsuzsa

    2005-09-30

    The effects of D-amino acids at Asp{sup 23} and Ser{sup 26} residues on the conformational preference of {beta}-amyloid (A{beta}) peptide fragment (A{beta}{sub 20-29}) have been studied using different spectroscopic techniques, namely vibrational circular dichroism (VCD), vibrational absorption, and electronic circular dichroism. To study the structure of the A{beta}{sub 20-29}, [D-Asp{sup 23}]A{beta}{sub 20-29}, and [D-Ser{sup 26}]A{beta}{sub 20-29} peptides under different conditions, the spectra were measured in 10 mM acetate buffer (pH 3) and in 2,2,2-trifluoroethanol (TFE). The spectroscopic results indicated that at pH 3, A{beta}{sub 20-29} peptide takes random coil with {beta}-turn structure, while [D-Ser{sup 26}]A{beta}{sub 20-29} peptide adopts significant amount of polyproline II (PPII) type structure along with {beta}-turn contribution and D-Asp-substituted peptide ([D-Asp{sup 23}]A{beta}{sub 20-29}) adopts predominantly PPII type structure. The increased propensity for PPII conformation upon D-amino acid substitution, in acidic medium, has important biological implications. In TFE, A{beta}{sub 20-29}, [D-Asp{sup 23}]A{beta}{sub 20-29}, and [D-Ser{sup 26}]A{beta}{sub 20-29} peptides adopt 3{sub 10}-helix, {alpha}-helix, and random coil with some {beta}-turn structures, respectively. The VCD data obtained for the A{beta} peptide films suggested that the secondary structures for the peptide films are not the same as those for corresponding solution and are also different among the A{beta} peptides studied here. This observation suggests that dehydration can have a significant influence on the structural preferences of these peptides.

  20. Components of yeast (Sacchromyces cervisiae) extract as defined media additives that support the growth and productivity of CHO cells.

    PubMed

    Spearman, Maureen; Chan, Sarah; Jung, Vince; Kowbel, Vanessa; Mendoza, Meg; Miranda, Vivian; Butler, Michael

    2016-09-10

    Yeast and plant hydrolysates are used as media supplements to support the growth and productivity of CHO cultures for biopharmaceutical production. Through fractionation of a yeast lysate and metabolic analysis of a fraction that had bioactivity equivalent to commercial yeast extract (YE), bioactive components were identified that promoted growth and productivity of two recombinant CHO cell lines (CHO-Luc and CHO-hFcEG2) equivalent to or greater than YE-supplemented media. Autolysis of the yeast lysate was not necessary for full activity, suggesting that the active components are present in untreated yeast cells. A bioactive fraction (3KF) of the yeast lysate was isolated from the permeate using a 3kDa molecular weight cut-off (MWCO) filter. Supplementation of this 3KF fraction into the base media supported growth of CHO-Luc cells over eight passages equivalent to YE-supplemented media. The 3KF fraction was fractionated further by a cation exchange spin column using a stepwise pH elution. Metabolomic analysis of a bioactive fraction isolated at high pH identified several arginine and lysine-containing peptides as well as two polyamines, spermine and spermidine, with 3.5× and 4.5× higher levels compared to a fraction showing no bioactivity. The addition of a mixture of polyamines and their precursors (putrescine, spermine, spermidine, ornithine and citrulline) as well as increasing the concentration of some of the components of the original base medium resulted in a chemically-defined (CD) formulation that produced an equivalent viable cell density (VCD) and productivity of the CHO-Luc cells as the YE-supplemented medium. The VCD of the CHO-hFcEG2 culture in the CD medium was 1.9× greater and with equivalent productivity to the YE-supplemented media.

  1. Conformational analysis and vibrational circular dichroism of tris(ethylenediamine)ruthenium(II) complex: a theoretical study.

    PubMed

    Pandith, Altaf Hussain; Pati, Swapan K

    2010-01-14

    The conformational preferences and vibrational circular dichroism of tris(ethylenediamine)ruthenium complex in two main configurations (Lambda) and (Delta), have been performed using density functional theory. We find that for the free [Ru(en)(3)](2+) ion in the Delta-configuration, the conformational stability order is Delta(deltadeltadelta) > Delta(lambdadeltadelta) > Delta(lambdalambdadelta) > Delta(lambdalambdalambda) and that for the Lambda-configuration it is Lambda(deltadeltadelta) < Lambda(lambdadeltadelta) < Lambda(lambdalambdadelta) < Lambda(lambdalambdalambda). The energy differences between the four conformers for both the configurations Delta and Lambda are relatively small, but the activation barriers for ring inversion from one conformation to another are significant, as compared to other such systems. We trace the origin of these results to the lower oxidation state of Ru and relatively larger Ru-N bond length. We have also studied the effect of counterions on the conformational stability for Ru(en)(3)Cl(2.) Our results indicate a reverse stability order for the associated complex, Ru(en)(3) Cl(2) and higher activation barriers for ring inversion as compared to the free complex ion Ru(en)(3)(2+). It is because of larger hydrogen bonding interactions between the three N-H bonds and the chloride ion in these two conformers as compared to other conformations, which is also evident from the VCD spectra of N-H stretching modes. We also investigate IR spectra for all conformations in Delta- and Lambda-configurations and together with energetics and VCD spectra elucidate the spectroscopic characteristics of Ru(en)(3)(2+) complexes with and without the associated counterions.

  2. The benefits of China's efforts on gaseous pollutant control indicated by the bottom-up emissions and satellite observation

    NASA Astrophysics Data System (ADS)

    Xia, Y.; Zhao, Y.

    2015-12-01

    To evaluate the effectiveness of national policies of air pollution control, the emissions of SO2, NOX, CO and CO2 in China are estimated with a bottom-up method from 2000 to 2014, and vertical column densities (VCD) from satellite observation are used to evaluate the inter-annual trends and spatial distribution of emissions and the temporal and spatial patterns of ambient levels of gaseous pollutants across the country. In particular, an additional emission case named STD case, which combines the most recent issued emission standards for specific industrial sources, is developed for 2012-2014. The inter-annual trends in emissions and VCDs match well except for SO2, and the revised emissions in STD case improve the comparison, implying the benefits of emission control for most recent years. Satellite retrieval error, underestimation of emission reduction and improved atmospheric oxidization caused the differences between emissions and VCDs trend of SO2. Coal-fired power plants play key roles in SO2 and NOX emission reduction. As suggested by VCD and emission inventory, the control of CO in 11th five year plan (FYP) period was more effective than that in the 12th FYP period, while the SO2 appeared opposite. As the new control target added in 12th FYP, NOX emissions have been clearly decreased 4.3 Mt from 2011 to 2014, in contrast to the fast growth before 2011. The inter-annual trends in NO2 VCDs has the poorest correlation with vehicle ownership (R=0.796), due to the staged emission standard of vehicles. In developed regions, transportation has become the main pollutants emission source and we prove this by comparing VCDs of NO2 to VCDs of SO2. Moreover, air quality in mega cities has been evaluated based on satellite observation and emissions, and results indicate that Beijing suffered heavily from the emissions from Hebei and Tianjin, while the local emissions tend to dominate in Shanghai.

  3. Postnatal Elongation of Eye Size in DBA/2J Mice Compared with C57BL/6J Mice: In Vivo Analysis with Whole-Eye OCT

    PubMed Central

    Chou, Tsung-Han; Kocaoglu, Omer P.; Borja, David; Ruggeri, Marco; Uhlhorn, Stephen R.; Manns, Fabrice

    2011-01-01

    Purpose. To characterize postnatal changes in eye size in glaucomatous DBA/2J (D2) mice and in nonglaucomatous C57BL/6J mice (B6) in vivo by means of whole-eye optical coherence tomography (OCT). Methods. D2 (n = 32) and B6 (n = 36) mice were tested between 2 and 20 months of age in eight age bins. A custom time-domain OCT system with a center wavelength of 825 nm and an axial scan length of 7.1 mm produced axial A-scan interferograms at a rate of 20 A-lines/s with a resolution of 8 μm. Axial length (AL), corneal thickness (CT), anterior chamber depth (ACD), lens thickness (LT), vitreous chamber depth (VCD), and retinal thickness (RT) were measured in the optical axis and adjusted with corresponding refractive indices. Corneal curvature (CC) and IOP were also measured. Results. AL increased (P < 0.001) more in the D2 (21%) than in the B6 (9%) mice. There was an interaction effect (two-way ANOVA, P < 0.001) between age and strain for AL, CT, ACD, and VCD. In the D2 mice, the lens became dislocated posteriorly. Multiple regression analysis in the D2 mice revealed an independent effect of age and IOP (P ≤ 0.01) on axial length. CC steepened in the older D2 mice, whereas it flattened in the B6 mice. Conclusions. In D2 mice, postnatal elongation of AL is larger than that in B6 mice and is associated with a greater increase in ACD and IOP, which seems to be a causal factor. The ease of use, short acquisition time, and noninvasiveness of whole-eye OCT make it suitable for routine use in longitudinal studies of mouse models. PMID:21372015

  4. Components of yeast (Sacchromyces cervisiae) extract as defined media additives that support the growth and productivity of CHO cells.

    PubMed

    Spearman, Maureen; Chan, Sarah; Jung, Vince; Kowbel, Vanessa; Mendoza, Meg; Miranda, Vivian; Butler, Michael

    2016-09-10

    Yeast and plant hydrolysates are used as media supplements to support the growth and productivity of CHO cultures for biopharmaceutical production. Through fractionation of a yeast lysate and metabolic analysis of a fraction that had bioactivity equivalent to commercial yeast extract (YE), bioactive components were identified that promoted growth and productivity of two recombinant CHO cell lines (CHO-Luc and CHO-hFcEG2) equivalent to or greater than YE-supplemented media. Autolysis of the yeast lysate was not necessary for full activity, suggesting that the active components are present in untreated yeast cells. A bioactive fraction (3KF) of the yeast lysate was isolated from the permeate using a 3kDa molecular weight cut-off (MWCO) filter. Supplementation of this 3KF fraction into the base media supported growth of CHO-Luc cells over eight passages equivalent to YE-supplemented media. The 3KF fraction was fractionated further by a cation exchange spin column using a stepwise pH elution. Metabolomic analysis of a bioactive fraction isolated at high pH identified several arginine and lysine-containing peptides as well as two polyamines, spermine and spermidine, with 3.5× and 4.5× higher levels compared to a fraction showing no bioactivity. The addition of a mixture of polyamines and their precursors (putrescine, spermine, spermidine, ornithine and citrulline) as well as increasing the concentration of some of the components of the original base medium resulted in a chemically-defined (CD) formulation that produced an equivalent viable cell density (VCD) and productivity of the CHO-Luc cells as the YE-supplemented medium. The VCD of the CHO-hFcEG2 culture in the CD medium was 1.9× greater and with equivalent productivity to the YE-supplemented media. PMID:27165505

  5. Analysis of volcanic bromine monoxide emissions in the southwestern Pacific region in 2005 based on satellite observations from OMI

    NASA Astrophysics Data System (ADS)

    Popp, Christoph; McCormick, Brendan; Suleiman, Raid; Chance, Kelly; Andrews, Benjamin; Cottrell, Elizabeth

    2015-04-01

    In this study, we analyze the potential of the Ozone Monitoring Instrument (OMI) for the detection and quantification of volcanic bromine monoxide (BrO) from space. Compared to other available UV/VIS satellite sensors with similar trace gas retrieval capability (like GOME-2) OMI has better spatial resolution and global coverage, likely leading to a better detection limit of BrO. In addition, the now more than ten years long OMI data record exceeds others in time and can be exploited for different volcanological applications. We chose the southwestern Pacific as our study region, including the Marianas, Papua New Guinea, and Vanuatu because volcanic activity of different magnitude has been reported in the Global Volcanism Program data base in this area. We analyze measurements acquired during the entire year of 2005. We use the standard level-2 OMI BrO data product available from NASA GES DISC. In addition, we take advantage of coincident OMI SO2 retrievals as a proxy for the plume extent and to calculate BrO/SO2 ratios. We explore spatial variations in BrO/SO2 ratios and interpret these in terms of atmospheric chemical processing. For example, the Anatahan eruption in March 2005 clearly reveals lower BrO/SO2 values closer to the source that increase downwind before leveling-off at a certain distance from the vent. We also report the first BrO measurements from several volcanoes in the southwestern Pacific, including Anatahan, Manam, and Bagana where the plume BrO vertical column densities (VCD) clearly exceed background values and where plume BrO and SO2 VCD are highly correlated (R>0.8). Finally, our analysis suggests that several volcanoes emitting BrO may have an as-yet unappreciated contribution to global halogen emissions from volcanoes.

  6. Detection from space of a reduction in anthropogenic emissions of nitrogen oxides during the Chinese economic downturn

    NASA Astrophysics Data System (ADS)

    Lin, J.-T.; McElroy, M. B.

    2011-08-01

    Rapid economic and industrial development in China and relatively weak emission controls have resulted in significant increases in emissions of nitrogen oxides (NOx) in recent years, with the exception of late 2008 to mid 2009 when the economic downturn led to emission reductions detectable from space. Here vertical column densities (VCDs) of tropospheric NO2 retrieved from satellite observations by SCIAMACHY, GOME-2 and OMI (both by KNMI and by NASA) are used to evaluate changes in emissions of NOx from October 2004 to February 2010 identifying impacts of the economic downturn. Data over polluted regions of Northern East China suggest an increase of 27-33 % in 12-month mean VCD of NO2 prior to the downturn, consistent with an increase of 49 % in thermal power generation (TPG) reflecting the economic growth. More detailed analysis is used to quantify changes in emissions of NOx in January over the period 2005-2010 when the effect of the downturn was most evident. The GEOS-Chem model is employed to evaluate the effect of changes in chemistry and meteorology on VCD of NO2. This analysis indicates that emissions decreased by 20 % from January 2008 to January 2009, close to the reduction of 18 % in TPG that occurred over the same interval. A combination of three independent approaches indicates that the economic downturn was responsible for a reduction in emissions by 9-11 % in January 2009 with an additional decrease of 10 % attributed to the slow-down in industrial activity associated with the coincident celebration of the Chinese New Year; errors in the estimate are most likely less than 3.4 %.

  7. Detection from space of a reduction in anthropogenic emissions of nitrogen oxides during the Chinese economic downturn

    NASA Astrophysics Data System (ADS)

    Lin, J.-T.; McElroy, M. B.

    2011-01-01

    Rapid economic and industrial development in China and relatively weak emission controls have resulted in significant increases in emissions of nitrogen oxides (NOx) in recent years, with the exception of late 2008 to mid 2009 when the economic downturn led to emission reductions detectable from space. Here vertical column densities (VCDs) of tropospheric NO2 retrieved from satellite observations by SCIAMACHY, GOME-2 and OMI (both by KNMI and by NASA) are used to evaluate changes in emissions of NOx from October 2004 to February 2010 identifying impacts of the economic downturn. Data over polluted regions of Northern East China suggest an increase of 27-33% in annual mean VCD of NO2 prior to the downturn, consistent with an increase of 49% in thermal power generation (TPG) reflecting the economic growth. More detailed analysis is used to quantify changes in emissions of NOx in January over the period 2005-2010 when the effect of the downturn was most evident. The GEOS-Chem model is employed to evaluate the effect of changes in chemistry and meteorology on VCD of NO2. This analysis indicates that emissions decreased by 20% from January 2008 to January 2009, close to the reduction of 18% in TPG that occurred over the same interval. A combination of three relatively independent approaches indicates that the economic downturn was responsible for a~reduction in emissions by 9-11% in January 2009 with an additional decrease of 10% attributed to the slow-down in industrial activity associated with the coincident celebration of the Chinese New Year.

  8. A New Derivative of Valproic Acid Amide Possesses a Broad-spectrum Antiseizure Profile and Unique Activity Against Status Epilepticus and Organophosphate Neuronal Damage

    PubMed Central

    White, H. Steve; Alex, Anitha B.; Pollock, Amanda; Hen, Naama; Shekh-Ahmad, Tawfeeq; Wilcox, Karen S.; McDonough, John H.; Stables, James P.; Kaufmann, Dan; Yagen, Boris; Bialer, Meir

    2011-01-01

    Summary Purpose sec-Butyl-propylacetamide (SPD) is a one-carbon homologue of valnoctamide (VCD), a CNS-active amide derivative of valproic acid (VPA) currently in phase II clinical trials. The current study evaluated the anticonvulsant activity of SPD in a battery of rodent seizure and epilepsy models and assessed its efficacy in rat and guinea pig models of status epilepticus (SE) and neuroprotection in an organotypic hippocampal slice model of excitotoxic cell death. Methods SPD’s anticonvulsant activity was evaluated in several rodent seizure and epilepsy models including: maximal electroshock (MES), 6Hz psychomotor, subcutaneous (s.c.) metrazol-, s.c., picrotoxin, s.c. bicuculline, audiogenic and corneal and hippocampal kindled seizures following intraperitoneal administration. Results obtained with SPD are discussed in relationship to those obtained with VPA and VCD. SPD was also evaluated for its ability to block benzodiazepine-resistant SE induced by pilocarpine (rats) and soman (rats and guinea pigs) following intraperitoneal administration. SPD was tested for its ability to block excitotoxic cell death induced by the glutamate agonists N-methyl-D-Aspartate (NMDA) and kainic acid (KA) using organotypic hippocampal slices and SE-induced hippocampal cell death using FluoroJade B staining. The cognitive function of SPD-treated rats that were protected against pilocarpine-induced convulsive SE was examined 10-14 days post SE using the Morris water maze (MWM). The relationship between the pharmacokinetic profile of SPD and its efficacy against soman-induced SE was evaluated in two parallel studies following SPD (60 mg/kg, i.p.) administration in the soman SE rat model. Key Findings SPD was highly effective and displayed a wide protective index (PI=TD50/ED50) in the standardized seizure and epilepsy models employed. SPD’s wide PI values demonstrate that it is effective at doses well below those that produce behavioral impairment. Unlike VCD, SPD also

  9. First measurements of formaldehyde integral content at Zvenigorod Scientific Station

    NASA Astrophysics Data System (ADS)

    Barouski, A. N.; Elokhov, A.; Postylyakov, O.; Kanaya, Y.

    2013-12-01

    We present the first observations of formaldehyde (HCHO) atmospheric column performed in Zvenigorod, Moscow Region, Russia. The data were retrieved from UV spectra of the scattered solar radiation measured by the MAX-DOAS instrument developed by JAMSTEC. We developed an algorithm for the HCHO retrieval from these spectra. For the HCHO differential slant column densities retrieval we used recommended by CINDI campaign DOAS settings (Pinardi et al, 2012). The slant column densities of HCHO were converted to the vertical column densities (VCD) using the air mass factor calculated by a radiative transfer model MCC++ (Postylyakov O.V., 2004). The determination of HCHO in the reference spectrum used multi-axis measurements. The variability of the HCHO vertical column in 2010 is analyzed. The HCHO vertical column density is larger during east wind directions than during non-east wind directions. It can be associated with Moscow Megacity influence on air quality at Zvenigorod. The estimation of Moscow Megacity influence on HCHO abundance at Zvenigorod is around 2.5 × 1014 mol/cm2 per 1 km length of trajectory path inside Moscow Ring Road. A temperature effect is noticeable in the HCHO VCD. Our data show statistically significant positive temperature effect in HCHO for the background condition for temperatures from -5C to +33C. The temperature trend in HCHO data at Zvenigorod Scientific Station is about (8.9×2.3)×1014 mol/cm2/C. The increase of the HCHO VCD during increase of the air temperature can be explained by the HCHO formation from non-methane volatile organic compounds for which more emission is expected at higher temperatures, especially from isoprene (Irie et al, 2011). This study was supported by RFBR under grants 12-05-92108 and 11-05-01175, and by JSPS under the Japan-Russia Research Cooperative Program. References. Irie H., Takashima H., Kanaya Y., Boersma K. F., Gast L., Wittrock F., Brunner D., Zhou Y. and Van Roozendael M.: Eight-component retrievals

  10. Conformations of [(R,R)-1,5-diaza-cis-decalin] copper (II) complex and its hydrogen bonding interaction with the crystal water: A combined experimental VA, UV-Vis and ECD spectroscopic and DFT study

    NASA Astrophysics Data System (ADS)

    Dezhahang, Zahra; Poopari, Mohammad Reza; Xu, Yunjie

    2012-09-01

    Chiral 1,5-diaza-cis-decalin ligand and its copper-complexes have found considerable applications in catalyzing enantioselective organic reactions. In the present article, (R,R)-1,5-diaza-cis-decalin ligand and its copper (II) hydroxide iodine hydrate complex have been investigated by using vibrational absorption (VA), ultraviolet-visible (UV-Vis), and electronic circular dichroism (ECD) experimental spectroscopic measurements, as well as density functional theory modeling. An extensive theoretical conformational analysis of the ligand has revealed that the ligand can adopt a good number of orientations in terms of its frame conformations, i.e. Chair-Chair, Chair-Boat, and Boat-Boat, the proximal (also denoted as in) and distal (out) positions for its two N atoms, and the equatorial (e) and axial (a) positions of its two amine H atoms. The most dominant conformation at room temperature was predicted to take on the Chair-Chair N-in H-ea configuration, based on the relative Gibbs free energy ordering at the B3LYP/6-31++G(d,p) level. The VA, vibrational CD, UV-Vis, and ECD spectra of the ligand conformers have been simulated. Conformational searches have also been carried out for the titled copper complex at the B3LYP/LanL2DZ level and the dominant conformer was predicted to have the Chair-Chair N-in H-ee configuration for its ligands, with a close to 100% Boltzmann population factor at room temperature. Furthermore, geometry optimizations and spectral simulations have been performed for the hydrogen bonded cluster of the complex with the crystal water. The effects of hydrogen bonding interaction with the crystal water on the VA, VCD, UV-Vis, and ECD spectra have been discussed. The interaction with the water molecule has been found to have significant impacts on the appearance of VA, VCD and ECD spectra and its inclusion is essential to obtain satisfactory interpretations of the experimental VA and ECD spectra.

  11. Effect of silver nanoparticle coatings on mycobacterial biofilm attachment and growth: Implications for ceramic water filters

    NASA Astrophysics Data System (ADS)

    Larimer, Curtis James

    Silver is a natural, broad-spectrum antibacterial metal and its toxicity can be enhanced when surface area is maximized. As a result, silver nanoparticles (AgNP) have been investigated for use in novel water treatment technologies. The hypothesis of this work is that deposited AgNPs can enhance water treatment technologies by inhibiting growth of planktonic bacteria and biofilms. This was investigated by evaluating the antibacterial efficacy of AgNPs both in solution and as deposited on surfaces. AgNPs were found to be toxic to three species of environmental mycobacteria, M. smegmatis, M. avium, and M. marinum and the level of susceptibility varied widely, probably owing to the varying levels of silver that each species is exposed to in its natural environment. When cultured in a AgNP enriched environment M. smegmatis developed resistance to the toxic effects of both the nanoparticles and silver ions. The resistant mutant was as viable as the unmodified strain and was also resistant to antibiotic isoniazid. However, the strain was more susceptible to other toxic metal ions from ZnSO4 and CuSO4. AgNPs were deposited on silicon wafer substrates by vertical colloidal deposition (VCD). Manipulating deposition speed and also concentration of AgNPs in the depositing liquid led to a range of AgNP coatings with distinctive deposition lines perpendicular to the motion of the meniscus. Experimental results for areal coverage, which was measured from SEM images of AgNP coatings, were compared to Diao's theory of VCD but did not show agreement due to a stick-slip mechanism that is not accounted for by the theory. Durability of AgNP coatings is critical for antibacterial efficacy and to mitigate the risks of exposing the environment to nanomaterials and it was measured by exposing AgNP coatings to liquid flow in a flow cell. Durability was improved by modifying processing to include a heat treatment after deposition. Finally, the antibiofilm efficacy of deposited AgNPs was

  12. Discrepancies between conformational distributions of a polyalanine peptide in solution obtained from molecular dynamics force fields and amide I' band profiles.

    PubMed

    Verbaro, Daniel; Ghosh, Indrajit; Nau, Werner M; Schweitzer-Stenner, Reinhard

    2010-12-30

    Structural preferences in the unfolded state of peptides determined by molecular dynamics still contradict experimental data. A remedy in this regard has been suggested by MD simulations with an optimized Amber force field ff03* ( Best, R. Hummer, G. J. Phys. Chem. B 2009 , 113 , 9004 - 9015 ). The simulations yielded a statistical coil distribution for alanine which is at variance with recent experimental results. To check the validity of this distribution, we investigated the peptide H-A(5)W-OH, which with the exception of the additional terminal tryptophan is analogous to the peptide used to optimize the force fields ff03*. Electronic circular dichroism, vibrational circular dichroism, and infrared spectroscopy as well as J-coupling constants obtained from NMR experiments were used to derive the peptide's conformational ensemble. Additionally, Förster resonance energy transfer between the terminal chromophores of the fluorescently labeled peptide analogue H-Dbo-A(5)W-OH was used to determine its average length, from which the end-to-end distance of the unlabeled peptide was estimated. Qualitatively, the experimental (3)J(H(N),C(α)), VCD, and ECD indicated a preference of alanine for polyproline II-like conformations. The experimental (3)J(H(N),C(α)) for A(5)W closely resembles the constants obtained for A(5). In order to quantitatively relate the conformational distribution of A(5) obtained with the optimized AMBER ff03* force field to experimental data, the former was used to derive a distribution function which expressed the conformational ensemble as a mixture of polyproline II, β-strand, helical, and turn conformations. This model was found to satisfactorily reproduce all experimental J-coupling constants. We employed the model to calculate the amide I' profiles of the IR and vibrational circular dichroism spectrum of A(5)W, as well as the distance between the two terminal peptide carbonyls. This led to an underestimated negative VCD couplet and an

  13. Infrared and vibrational CD spectra of partially solvated alpha-helices: DFT-based simulations with explicit solvent.

    PubMed

    Turner, David R; Kubelka, Jan

    2007-02-22

    Theoretical simulations are used to investigate the effects of aqueous solvent on the vibrational spectra of model alpha-helices, which are only partly exposed to solvent to mimic alpha-helices in proteins. Infrared absorption (IR) and vibrational circular dichroism (VCD) amide I' spectra for 15-amide alanine alpha-helices are simulated using density functional theory (DFT) calculations combined with the property transfer method. The solvent is modeled by explicit water molecules hydrogen bonded to the solvated amide groups. Simulated spectra for two partially solvated model alpha-helices, one corresponding to a more exposed and the other to a more buried structure, are compared to the fully solvated and unsolvated (gas phase) simulations. The dependence of the amide I spectra on the orientation of the partially solvated helix with respect to the solvent and effects of solvation on the amide I' of 13C isotopically substituted alpha-helices are also investigated. The partial exposure to solvent causes significant broadening of the amide I' bands due to differences in the vibrational frequencies of the explicitly solvated and unsolvated amide groups. The different degree of partial solvation is reflected primarily in the frequency shifts of the unsolvated (buried) amide group vibrations. Depending on which side of the alpha-helix is exposed to solvent, the simulated IR band-shapes exhibit significant changes, from broad and relatively featureless to distinctly split into two maxima. The simulated amide I' VCD band-shapes for the partially solvated alpha-helices parallel the broadening of the IR and exhibit more sign variation, but generally preserve the sign pattern characteristic of the alpha-helical structures and are much less dependent on the alpha-helix orientation with respect to the solvent. The simulated amide I' IR spectra for the model peptides with explicitly hydrogen-bonded water are consistent with the experimental data for small alpha-helical proteins

  14. Rain-induced emission pulses of NOx and HCHO from soils in African regions after dry spells as viewed by satellite sensors

    NASA Astrophysics Data System (ADS)

    Zörner, Jan; Penning de Vries, Marloes; Beirle, Steffen; Veres, Patrick; Williams, Jonathan; Wagner, Thomas

    2014-05-01

    for higher resolution grid boxes to map the spatial pattern of absolute and relative enhancements after the wetting of dry soils. At the beginning of the wet season in the Sahel in April/May/June strong NO2 VCD enhancements compared to the background levels are observed by all three satellite sensors. A significant enhancement in HCHO VCD is also detected with GOME-2. Further analysis shows that spatial patterns and the magnitude of such enhancements over Africa are highly dependent on the season, prevailing temperatures and land cover types.

  15. Theoretical investigations into spectral and non-linear optical properties of brucine and strychnine using density functional theory

    NASA Astrophysics Data System (ADS)

    Islam, Nasarul; Niaz, Saba; Manzoor, Taniya; Pandith, Altaf Hussain

    2014-10-01

    The density functional theoretical (DFT) computations were performed at the B3LYP/6-311G++(d, p) level to calculate the equilibrium geometry, vibrational wave numbers, intensities, and various other molecular properties of brucine and strychnine, which were found in satisfactory agreement with the experimental data. The out-of-phase stretching modes of aromatic rings and carbonyl stretching modes in combination with CH stretching modes at stereogenic centers generate VCD signals, which are remarkably efficient configuration markers for these chiral molecular systems. NBOs analysis reveals that the large values of second order perturbation energy (47.24 kcal/mol for brucine and 46.93 kcal/mol for strychnine) confirms strong hyperconjugative interaction between the orbital containing the lone pair of electron of nitrogen and the neighboring Cdbnd O antibonding orbital. The molecular electrostatic potential map of strychnine molecule, with no polar groups other than the lone keto group, shows less polarization, which accounts for its lower susceptibility towards electrophilic attack as compared to brucine.

  16. The role of computerized modeling and simulation in the development of life support system technologies.

    PubMed

    Modell, M; Evanich, P; Chen, C C; Anavi, S; Mai, J

    1989-01-01

    Using conventional means of process development, it would take decades and hundreds of millions of dollars to develop technology for recycling of water and solid waste for lunar missions within the next thirty years. Since we anticipate neither that amount of time nor level of funding, new methodologies for developing life support systems (LSS) technologies are essential. Computerized modeling and simulation (CMAS) is a tool that can greatly reduce both the time and cost of technology development. By CMAS, we refer to computer methods for correlating, storing and retrieving property data for chemical species and for solving the phenomenological equations of physical/chemical processes (i.e., process conditions based on properties of materials and mass and energy balances, equipment sizing based on rate processes and the governing equations for unit operations). In particular, CMAS systems can be used to evaluate a LSS process design with minimal requirements for laboratory experimentation. A CMAS model using ASPEN PLUS is presented for a vapor compression distillation (VCD) system designed for reclaiming water from urine.

  17. Spatial variance and assessment of nitrogen dioxide pollution in major cities of Pakistan along N5-Highway.

    PubMed

    Shabbir, Yasir; Khokhar, Muhammad Fahim; Shaiganfar, Reza; Wagner, Thomas

    2016-05-01

    This paper discusses the findings of the first car MAX-DOAS (multi-axis differential optical absorption spectroscopy) field campaign (300km long) along the National Highway-05 (N5-Highway) of Pakistan conducted on 13 and 14 November, 2012. The main objective of the field campaign was to assess the spatial distribution of tropospheric nitrogen dioxide (NO2) columns and corresponding concentrations along the N5-Highway from Islamabad to Lahore. Source identification of NO2 revealed that the concentrations were higher within major cities along the highway. The highest NO2 vertical column densities (NO2 VCDs) were found around two major cities of Rawalpindi and Lahore. This study also presents a comparison of NO2 VCDs measured by the ozone monitoring instrument (OMI) and car MAX-DOAS observations. The comparison revealed similar spatial distribution of the NO2 columns with both car MAX-DOAS and satellite observations, but the car MAX-DOAS observations show much more spatial details. Maximum NO2 VCD retrieved from car MAX-DOAS observations was up to an order of magnitude larger than the OMI observations in urban areas.

  18. Revising the slant column density retrieval of nitrogen dioxide observed by the Ozone Monitoring Instrument

    NASA Astrophysics Data System (ADS)

    Marchenko, S.; Krotkov, N. A.; Lamsal, L. N.; Celarier, E. A.; Swartz, W. H.; Bucsela, E. J.

    2015-06-01

    Nitrogen dioxide retrievals from the Aura/Ozone Monitoring Instrument (OMI) have been used extensively over the past decade, particularly in the study of tropospheric air quality. Recent comparisons of OMI NO2 with independent data sets and models suggested that the OMI values of slant column density (SCD) and stratospheric vertical column density (VCD) in both the NASA OMNO2 and Royal Netherlands Meteorological Institute DOMINO products are too large, by around 10-40%. We describe a substantially revised spectral fitting algorithm, optimized for the OMI visible light spectrometer channel. The most important changes comprise a flexible adjustment of the instrumental wavelength shifts combined with iterative removal of the ring spectral features; the multistep removal of instrumental noise; iterative, sequential estimates of SCDs of the trace gases in the 402-465 nm range. These changes reduce OMI SCD(NO2) by 10-35%, bringing them much closer to SCDs retrieved from independent measurements and models. The revised SCDs, submitted to the stratosphere-troposphere separation algorithm, give tropospheric VCDs ˜10-15% smaller in polluted regions, and up to ˜30% smaller in unpolluted areas. Although the revised algorithm has been optimized specifically for the OMI NO2 retrieval, our approach could be more broadly applicable.

  19. Association between Refractive Errors and Ocular Biometry in Iranian Adults

    PubMed Central

    Hashemi, Hassan; Khabazkhoob, Mehdi; Emamian, Mohammad Hassan; Shariati, Mohammad; Miraftab, Mohammad; Yekta, Abbasali; Ostadimoghaddam, Hadi; Fotouhi, Akbar

    2015-01-01

    Purpose: To investigate the association between ocular biometrics such as axial length (AL), anterior chamber depth (ACD), lens thickness (LT), vitreous chamber depth (VCD) and corneal power (CP) with different refractive errors. Methods: In a cross-sectional study on the 40 to 64-year-old population of Shahroud, random cluster sampling was performed. Ocular biometrics were measured using the Allegro Biograph (WaveLight AG, Erlangen, Germany) for all participants. Refractive errors were determined using cycloplegic refraction. Results: In the first model, the strongest correlations were found between spherical equivalent with axial length and corneal power. Spherical equivalent was strongly correlated with axial length in high myopic and high hyperopic cases, and with corneal power in high hyperopic cases; 69.5% of variability in spherical equivalent was attributed to changes in these variables. In the second model, the correlations between vitreous chamber depth and corneal power with spherical equivalent were stronger in myopes than hyperopes, while the correlations between lens thickness and anterior chamber depth with spherical equivalent were stronger in hyperopic cases than myopic ones. In the third model, anterior chamber depth + lens thickness correlated with spherical equivalent only in moderate and severe cases of hyperopia, and this index was not correlated with spherical equivalent in moderate to severe myopia. Conclusion: In individuals aged 40-64 years, corneal power and axial length make the greatest contribution to spherical equivalent in high hyperopia and high myopia. Anterior segment biometric components have a more important role in hyperopia than myopia. PMID:26730304

  20. Characterizing Variability in the Spatial Distribution of Bromine Explosion Events in the Vicinity of Barrow, Alaska

    NASA Astrophysics Data System (ADS)

    Peterson, P.; Pratt, K.; Simpson, W. R.; Shepson, P. B.; Pöhler, D.; Friess, U.; Zielcke, J.; Platt, U.; Nghiem, S. V.; Sihler, H.

    2015-12-01

    Reactive halogens (e.g. Br, BrO) are produced photochemically during springtime in the Arctic. Some dramatic effects of these halogen species are known (e.g. ozone depletion, mercury deposition), but changes in atmospheric composition related to this halogen chemistry, particularly those related to increasing sea ice loss and the transformation of Arctic sea ice cover, are unknown. In March 2012, the Bromine, Ozone, Mercury EXperiment (BROMEX) provided an opportunity to enhance our understanding of the spatial and temporal variability of halogen chemistry in the vicinity of Barrow, Alaska. During BROMEX, we used Multiple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) to measure BrO lower tropospheric vertical column densities (LT-VCD) and near-surface mixing ratios at Barrow, as well as on land-fast ice 40 km north east of Barrow, and a drifting platform on seasonal sea ice west of Barrow. Concurrently, an aircraft equipped with the Heidelberg Airborne Imaging DOAS Instrument (HAIDI) collected airborne BrO data at altitudes up to 3 km. These measurements showed several instances of spatial gradients in BrO between measurement sites, as well as times when BrO was present up to 1km aloft. We explore explanations for these features using local and synoptic meteorology, back-trajectory modelling, MODIS and airborne imagery, as well as satellite-instrument-based maps of synoptic sea ice classes and tropospheric BrO.

  1. Development of a digital mobile solar tracker

    NASA Astrophysics Data System (ADS)

    Baidar, Sunil; Kille, Natalie; Ortega, Ivan; Sinreich, Roman; Thomson, David; Hannigan, James; Volkamer, Rainer

    2016-03-01

    We have constructed and deployed a fast digital solar tracker aboard a moving ground-based platform. The tracker consists of two rotating mirrors, a lens, an imaging camera, and a motion compensation system that provides the Euler angles of the mobile platform in real time. The tracker can be simultaneously coupled to UV-Vis and Fourier transform infrared spectrometers, making it a versatile tool to measure the absorption of trace gases using solar incoming radiation. The integrated system allows the tracker to operate autonomously while the mobile laboratory is in motion. Mobile direct sun differential optical absorption spectroscopy (mobile DS-DOAS) observations using this tracker were conducted during summer 2014 as part of the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) in Colorado, USA. We demonstrate an angular precision of 0.052° (about 1/10 of the solar disk diameter) during research drives and verify this tracking precision from measurements of the center to limb darkening (CLD, the changing appearance of Fraunhofer lines) in the mobile DS-DOAS spectra. The high photon flux from direct sun observation enables measurements of nitrogen dioxide (NO2) slant columns with high temporal resolution and reveals spatial detail in the variations of NO2 vertical column densities (VCDs). The NO2 VCD from DS-DOAS is compared with a co-located MAX-DOAS instrument. Overall good agreement is observed amid a highly heterogeneous air mass.

  2. Development of a digital mobile solar tracker

    NASA Astrophysics Data System (ADS)

    Baidar, S.; Kille, N.; Ortega, I.; Sinreich, R.; Thomson, D.; Hannigan, J.; Volkamer, R.

    2015-11-01

    We have constructed and deployed a fast digital solar tracker aboard a moving ground-based platform. The tracker consists of two rotating mirrors, a lens, an imaging camera, and a motion compensation system that provides the Euler angles of the mobile platform in real time. The tracker can be simultaneously coupled to UV-Vis and FTIR spectrometers making it a versatile tool to measure the absorption of trace gases using solar incoming radiation. The integrated system allows the tracker to operate autonomously while the mobile laboratory is in motion. Mobile direct sun Differential Optical Absorption Spectroscopy (mobile DS-DOAS) observations using this tracker were conducted during summer 2014 as part of the Front Range Photochemistry and Pollution Experiment (FRAPPE) in Colorado, USA. We demonstrate an angular precision of 0.052° (about 1/10 of the solar disk diameter) during research drives, and verify this tracking precision from measurements of the center to limb darkening (CLD, the changing appearance of Fraunhofer lines) in the mobile DS-DOAS spectra. The high photon flux from direct sun observation enables measurements of nitrogen dioxide (NO2) slant columns with high temporal resolution, and reveals spatial detail in the variations of NO2 vertical column densities (VCDs). The NO2 VCD from DS-DOAS is compared with a co-located MAX-DOAS instrument. Overall good agreement is observed amid a highly heterogeneous air mass.

  3. The role of computerized modeling and simulation in the development of life support system technologies.

    PubMed

    Modell, M; Evanich, P; Chen, C C; Anavi, S; Mai, J

    1989-01-01

    Using conventional means of process development, it would take decades and hundreds of millions of dollars to develop technology for recycling of water and solid waste for lunar missions within the next thirty years. Since we anticipate neither that amount of time nor level of funding, new methodologies for developing life support systems (LSS) technologies are essential. Computerized modeling and simulation (CMAS) is a tool that can greatly reduce both the time and cost of technology development. By CMAS, we refer to computer methods for correlating, storing and retrieving property data for chemical species and for solving the phenomenological equations of physical/chemical processes (i.e., process conditions based on properties of materials and mass and energy balances, equipment sizing based on rate processes and the governing equations for unit operations). In particular, CMAS systems can be used to evaluate a LSS process design with minimal requirements for laboratory experimentation. A CMAS model using ASPEN PLUS is presented for a vapor compression distillation (VCD) system designed for reclaiming water from urine. PMID:11537381

  4. An overview of ISS ECLSS life testing at NASA, MSFC.

    PubMed

    Tatara, J D; Roman, M C

    1998-01-01

    Numerous components have been developed for use in the International Space Station (ISS) Environmental Control and Life Support System (ECLSS). Although these components have performed admirably for short-duration subsystem tests, there is little long-range operational (life test) data available. It is important to know not only how long a subsystem is anticipated to perform, but also the problems that can be expected should subsystem components fail. For this reason, the National Aeronautics and Space Administration (NASA) at the Marshall Space Flight Center (MSFC) developed the ECLSS Life Test program. To date, assemblies and subassemblies that are being or have been tested include the Trace Contaminant Control Subassembly (TCCS), the Vapor Compression Distillation Urine Processor Assembly (VCD-UPA), the Four-Bed Molecular Sieve Carbon Dioxide Removal Assembly (4BMS-CDRA), and the Solid Polymer Electrolyzer Oxygen Generation Assembly (SPE-OGA). Also included in life testing are noncomponent life test studies. These include the Water Degradation Study and the Biofilm Life Test. The Water Degradation Study looks at water quality changes after exposure to simulated ISS pre-Water Recovery Management (WRM) conditions. The Biofilm Life Test will examine microbial accumulation on surfaces in a simulated ISS water delivery system. This article will briefly review the objectives of each life test program, the results of completed tests, and the major problems observed during the tests. PMID:11540459

  5. A Water Recovery System Evolved for Exploration

    NASA Technical Reports Server (NTRS)

    ORourke, Mary Jane E.; Perry, Jay L.; Carter, Donald L.

    2006-01-01

    A new water recovery system designed towards fulfillment of NASA's Vision for Space Exploration is presented. This water recovery system is an evolution of the current state-of-the-art system. Through novel integration of proven technologies for air and water purification, this system promises to elevate existing technology to higher levels of optimization. The novel aspect of the system is twofold: Volatile organic contaminants will be removed from the cabin air via catalytic oxidation in the vapor phase, prior to their absorption into the aqueous phase, and vapor compression distillation technology will be used to process the condensate and hygiene waste streams in addition to the urine waste stream. Oxidation kinetics dictate that removal of volatile organic contaminants from the vapor phase is more efficient. Treatment of the various waste streams by VCD will reduce the load on the expendable ion exchange and adsorption media which follow, and on the aqueous-phase volatile removal assembly further downstream. Incorporating these advantages will reduce the weight, volume, and power requirements of the system, as well as resupply.

  6. Metolachlor stereoisomers: Enantioseparation, identification and chiral stability.

    PubMed

    Xie, Jingqian; Zhang, Lijuan; Zhao, Lu; Tang, Qiaozhi; Liu, Kai; Liu, Weiping

    2016-09-01

    Metolachlor is a chiral herbicide consisting of four stereoisomers, which is typically used as a racemic mixture or is enriched with the herbicidally active 1'S-isomers. Because studies on the enantioselective behavior of phyto-biochemical processes and the environmental fate of metolachlor have become significant, a practical method for analyzing and separating metolachlor stereoisomers must be developed. In the present study, the enantiomeric separation of metolachlor was achieved using OD-H, AS-H, OJ-H and AY-H chiral columns. The effects of different organic modifiers in an n-hexane-based mobile phase were investigated, and various temperatures and flow rates, which may influence metolachlor separation, were also explored. The optimal resolution was obtained using an AY-H column with n-hexane/EtOH (96/4) as the mobile phase at a rate and temperature of 0.6mLmin(-1) and 25°C, respectively. The absolute configuration of the four stereoisomers was identified as αSS, αRS, αSR, αRR using computed and experimentally measured ECD and VCD spectra. Thermal interconversion and solvent stability experiments were also performed. Pure metolachlor stereoisomers in different organic solvents and water at 4°C or 30°C were stable. These results were used to establish a sound method for analyzing, preparing, characterizing, and preserving individual metolachlor stereoisomers in most natural environments. PMID:27544750

  7. Dynamic Modeling of Process Technologies for Closed-Loop Water Recovery Systems

    NASA Technical Reports Server (NTRS)

    Allada, Rama Kumar; Lange, Kevin; Anderson, Molly

    2011-01-01

    Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents dynamic simulations of chemical process for primary processor technologies including: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system, the Wiped-Film Rotating Disk (WFRD), and post-distillation water polishing processes such as the Volatiles Removal Assembly (VRA) that were developed using the Aspen Custom Modeler and Aspen Plus process simulation tools. The results expand upon previous work for water recovery technology models and emphasize dynamic process modeling and results. The paper discusses system design, modeling details, and model results for each technology and presents some comparisons between the model results and available test data. Following these initial comparisons, some general conclusions and forward work are discussed.

  8. Dynamic Modeling of Process Technologies for Closed-Loop Water Recovery Systems

    NASA Technical Reports Server (NTRS)

    Allada, Rama Kumar; Lange, Kevin E.; Anderson, Molly S.

    2012-01-01

    Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents dynamic simulations of chemical process for primary processor technologies including: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system, the Wiped-Film Rotating Disk (WFRD), and post-distillation water polishing processes such as the Volatiles Removal Assembly (VRA). These dynamic models were developed using the Aspen Custom Modeler (Registered TradeMark) and Aspen Plus(Registered TradeMark) process simulation tools. The results expand upon previous work for water recovery technology models and emphasize dynamic process modeling and results. The paper discusses system design, modeling details, and model results for each technology and presents some comparisons between the model results and available test data. Following these initial comparisons, some general conclusions and forward work are discussed.

  9. The role of computerized modeling and simulation in the development of life support system technologies

    NASA Astrophysics Data System (ADS)

    Modell, Michael; Evanich, Peggy; Chen, Chau-Chyun; Anavi, Selim; Mai, Jeff

    Using conventional means of process development, it would take decades and hundreds of millions of dollars to develop technology for recycling of water and solid waste for lunar missions within the next thirty years. Since we anticipate neither that amount of time nor level of funding, new methodologies for developing life support systems (LSS) technologies are essential. Computerized modeling and simulation (CMAS) is a tool that can greatly reduce both the time and cost of technology development. By CMAS, we refer to computer methods for correlating, storing and retrieving property data for chemical species and for solving the phenomenological equations of physical/chemical processes (i.e., process conditions based on properties of materials and mass and energy balances, equipment sizing based on rate processes and the governing equations for unit operations). In particular, CMAS systems can be used to evaluate a LSS process design with minimal requirements for laboratory experimentation. A CMAS model using ASPEN PLUS is presented for a vapor compression distillation (VCD) system designed for reclaiming water from urine.

  10. Hyperconjugative and Electrostatic Interactions as Anomeric Triggers in Archetypical 1,4-Dioxane Derivatives.

    PubMed

    Ortega, Pilar Gema Rodríguez; Montejo, Manuel; López González, Juan Jesús

    2016-02-16

    The anomeric effect accounts for the greater thermodynamic stability of axially arranged six-membered heterocycles holding an electronegative substituent at the C1 position. Within a frame of no general consensus, two different theories are typically claimed to justify this effect mostly based on either hyperconjugative or electrostatic factors. Here we report a theoretical-experimental study of the role of both as anomeric triggers in two archetypical 1,4-dioxane derivatives, using a suitable combination of spectroscopic (IR and vibrational circular dichroism) and computational techniques for the analysis of the solvation environment effect in their anomeric choices. VCD and IR spectroscopies are used as conformer-discriminating tools: a detailed analysis of the evolution of the spectral profiles allows assessing the theoretically predicted changes in the experimental α/β ratios when changing the polar solvent, which are fully explained on the basis of an extensive NBO energy partition scheme that provides a detailed view of the role of hyperconjugative and electrostatic interactions as anomeric regulators. Our results suggest that the anomeric equilibrium cannot be described by a single stereoelectronic effect but by the combined contribution of hyperconjugation and electrostatic repulsions, so that the β-anomeric choice in polar solvents is markedly driven by the strong attenuation of electrostatic repulsive interactions that occurs in solution. PMID:26663638

  11. Large variations in ocular dimensions in a multiethnic population with similar genetic background

    PubMed Central

    Niu, Zhiqiang; Li, Jun; Zhong, Hua; Yuan, Zhonghua; Zhou, Hua; Zhang, Yang; Yuan, Yuansheng; Chen, Qin; Pan, Chen-Wei

    2016-01-01

    We aimed to describe the ethnic variations in ocular dimensions among three ethnic groups with similar genetic ancestry from mainland of China. We included 2119 ethnic Bai, 2202 ethnic Yi and 2183 ethnic Han adults aged 50 years or older in the study. Ocular dimensions including axial length (AL), anterior chamber depth (ACD), vitreous chamber depth (VCD) and lens thickness (LT) were measured using A-scan ultrasonography. Bai Chinese had longer ALs (P < 0.001), deeper ACDs (P < 0.001) but shallower VCDs (P < 0.001) compared with the other two ethnic groups. There were no ethnic variations in LTs. Diabetes was associated with shallower ACDs and this association was stronger in Bai Chinese compared with Yi or Han Chinese (P for interaction = 0.02). Thicker lenses were associated with younger age (P = 0.04), male gender (P < 0.001), smoking history (P = 0.01), alcohol intake (P = 0.03), the presence of cataract (P < 0.001), and the presence of diabetes (P < 0.001). There were significant differences in ocular dimensions among different ethnic groups with small differences in genetics but large variations in cultures and lifestyles. PMID:26947903

  12. DFT investigation on dihydrogen-bonded amine-borane complexes.

    PubMed

    Yan, Shihai; Zou, Hongmei; Kang, Wukui; Sun, Lixiang

    2016-01-01

    The DFT method has been employed in the exploration on dihydrogen-bonded amine-borane complexes, with a special emphasis on the dimerization and substituent group effect. Stable dihydrogen bonded complexes can be generated from these amine-borane monomers with the appearance of NH(δ+)…H(δ-)B interactions. The binding energy decreases gradually with the increase of the steric effect of the substituents. The substituent group number mainly varies the C-N bond length. The dimerization generates close H…H and influences predominantly the N-B distance. The effect of dimerization on IR and vibrational circular dichroism (VCD) spectra is stronger than that of the number of substituent groups, which leads to distinct NBO charge variation on α-C. Both the substituent group number and dimerization enhance the chemical shift difference between hydrogen atoms covalently bonded to N and B, Δδ H-H, which can be hired as an index for structural determination. It is proposed that amine-borane complexes with more substituent groups in higher degree of polymerization are potentially interesting materials for hydrogen storage. Graphical Abstract Both the number of substituent group and dimerization enhance the chemical shift difference of hydrogen atoms covalently bonded on N and B, Δδ H-H, which can be employed as an index for the structural determination.

  13. MAX-DOAS observations of the total atmospheric water vapour column and comparison with independent observations

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Andreae, M. O.; Beirle, S.; Dörner, S.; Mies, K.; Shaiganfar, R.

    2013-01-01

    We developed an algorithm for the retrieval of the atmospheric water vapour column from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in the yellow and red spectral range. The retrieval is based on the so-called geometric approximation and does not depend on explicit a priori information for individual observations, extensive radiative transfer simulations, or the construction of large look-up tables. Disturbances of the radiative transfer due to aerosols and clouds are simply corrected using the simultaneously measured absorptions of the oxygen dimer, O4. We applied our algorithm to MAX-DOAS observations made at the Max Planck Institute for Chemistry in Mainz, Germany, from March to August 2011, and compared the results to independent observations. Good agreement with Aerosol Robotic Network (AERONET) and European Centre for Medium-Range Weather Forecasting (ECMWF) H2O vertical column densities (VCDs) is found, while the agreement with satellite observations is less good, most probably caused by the shielding effect of clouds for the satellite observations. Good agreement is also found with near-surface in situ observations, and it was possible to derive average daily H2O scale heights (between 1.5 km and 3 km). MAX-DOAS measurements use cheap and simple instrumentation and can be run automatically. One important advantage of our algorithm is that the H2O VCD can be retrieved even under cloudy conditions (except clouds with very high optical thickness).

  14. MAX-DOAS observations of the total atmospheric water vapour column and comparison with independent observations

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Andreae, M. O.; Beirle, S.; Dörner, S.; Mies, K.; Shaiganfar, R.

    2012-09-01

    We developed an algorithm for the retrieval of the atmospheric water vapour column from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in the yellow and red spectral range. The retrieval is based on the so called geometric approximation and does not depend on a-priori information, extensive radiative transfer simulations, or the construction of large look-up tables. Disturbances of the radiative transfer due to aerosols and clouds are simply corrected using the simultaneously measured absorptions of the oxygen dimer, O4. We applied our algorithm to MAX-DOAS observations made at the Max Planck Institute for Chemistry in Mainz, Germany, from March to August 2011 and compared the results to independent observations. Good agreement with Aerosol Robotic Network (AERONET) and European Centre for Medium-Range Weather Forecasting (ECMWF) H2O vertical column densities (VCDs) is found, while the agreement with satellite observations is less good, most probably caused by the shielding effect of clouds for the satellite observations. Good agreement is also found with near-surface in-situ observations, and it was possible to derive average daily H2O layer heights (between 1.5 km and 3 km). MAX-DOAS measurements use cheap and simple instrumentation and can be run automatically. One important advantage of our algorithm is that the H2O VCD can be retrieved even under cloudy conditions (except clouds with very high optical thickness).

  15. Structure-activity relationship study of selective excitatory amino acid transporter subtype 1 (EAAT1) inhibitor 2-amino-4-(4-methoxyphenyl)-7-(naphthalen-1-yl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (UCPH-101) and absolute configurational assignment using infrared and vibrational circular dichroism spectroscopy in combination with ab initio Hartree-Fock calculations.

    PubMed

    Huynh, Tri H V; Shim, Irene; Bohr, Henrik; Abrahamsen, Bjarke; Nielsen, Birgitte; Jensen, Anders A; Bunch, Lennart

    2012-06-14

    The excitatory amino acid transporters (EAATs) play essential roles in regulating the synaptic concentration of the neurotransmitter glutamate in the mammalian central nervous system. To date, five subtypes have been identified, named EAAT1-5 in humans, and GLAST, GLT-1, EAAC1, EAAT4, and EAAT5 in rodents, respectively. In this paper, we present the design, synthesis, and pharmacological evaluation of seven 7-N-substituted analogues of UCPH-101/102. Analogue 9 inhibited EAAT1 in the micromolar range (IC(50) value 20 μM), whereas analogues 8 and 10 were inactive (IC(50) values >100 μM). The diastereomeric pairs 11a/11b and 12a/12b were separated by HPLC and the absolute configuration assigned by VCD technique in combination with ab initio Hartree-Fock calculations. Analogues 11a (RS-isomer) and 12b (RR-isomer) inhibited EAAT1 (IC(50) values 5.5 and 3.8 μM, respectively), whereas analogues 11b (SS-isomer) and 12a (SR-isomer) failed to inhibit EAAT1 uptake (IC(50) values >300 μM). PMID:22594609

  16. The structure of tri-proline in water probed by polarized Raman, Fourier transform infrared, vibrational circular dichroism, and electric ultraviolet circular dichroism spectroscopy.

    PubMed

    Schweitzer-Stenner, Reinhard; Eker, Fatma; Perez, Alejandro; Griebenow, Kai; Cao, Xiaolin; Nafie, Laurence A

    2003-01-01

    Tripeptidesserve as model systems for understanding the so-called random-coil state of peptides and proteins. While it is well known that polyproline or proline-rich polypeptides adopt the very regular polyproline-II (PPII) or left-handed 3(1)-helix conformation, it was thus far not clear whether this is also the predominant structure adopted by proline-containing tripeptides. To clarify this issue, we have investigated the amide I' band profile in the ir, isotropic, and anisotropic Raman, and vibrational circular dichroism (VCD) spectrum of cationic and zwitterionic tri-proline in D(2)O. The data were analyzed by modifying a recently developed algorithm, which allows one to obtain the central dihedral angles of tripeptides from the amide I' band intensities (R. Schweitzer-Stenner, Biophysical Journal, 2002, Vol. 83, pp. 523-532). Our analysis revealed that the peptide adopts a nearly canonical PPII structure in water with psi and phi values in the range of 175 degrees -165 degrees and -70 degrees -(-80 degrees ), respectively. This is fully confirmed by the respective electronic ultraviolet-CD spectra. Our result indicates that the strong PPII propensity of trans proline results from local interactions between the pyrrolidine ring and the backbone and is not due to any long-range interactions.

  17. Insight into the packing pattern of β2 fibrils: a model study of glutamic acid rich oligomers with 13C isotopic edited vibrational spectroscopy.

    PubMed

    Chi, Heng; Welch, William R W; Kubelka, Jan; Keiderling, Timothy A

    2013-11-11

    Polyglutamic acid at low pH forms aggregates and self-assembles into a spiral, fibril-like superstructure formed as a β2-type sheet conformation that has a more compact intersheet packing than commonly found. This is stabilized by three-centered bifurcated hydrogen bonding of the amide carbonyl involving the protonated glutamic acid side chain. We report vibrational spectroscopic results and analyses for oligopeptides rich in glutamic acid enhanced with (13)C isotope labeling in a study modeling low pH poly-Glu self-assembly. Our results indicate bifurcated H-bonding and β2 aggregation can be attained in these model decamers, confirming they have the same conformations as poly-Glu. We also prepared conventional β1-sheet aggregates by rapid precipitation from the residual peptides in the higher pH supernatant. By comparing the isotope-enhanced IR and VCD spectra with theoretical predictions, we deduced that the oligo-Glu β2 structure is based on stacked, twisted, antiparallel β-sheets. The best fit to theoretical predictions was obtained for the strands being out of register, sequentially stepped by one residue, in a ladder-like fashion. The alternate β1 conformer for this oligopeptide was similarly shown to be antiparallel but was less ordered and apparently had a different registry in its aggregate structure.

  18. VCL: a high performance virtual CD library server

    NASA Astrophysics Data System (ADS)

    Wan, Jiguang; Xie, ChangSheng; Tan, Zhihu

    2005-09-01

    With the increasing of CD data in internet, CD mirror server has become the new technology. Considering the performance requirement of the traditional CD mirror server, we present a novel high performance VCL (Virtual CD Library) server. What makes VCL server superior is the two patented technologies: a new caching architecture and an efficient network protocol specifically tailored to VCL applications. VCL server is built based on an innovative caching technology. It employs a two-level cache structure on both a client side and the server side. Instead of using existing network and file protocols such as SMB/CIFS etc that are generally used by existing CD server, we have developed a set of new protocols specifically suitable to VCL environment. The new protocol is a native VCL protocol built directly on TCP/IP protocol. VCL protocol optimizes data transfer performance for block level data as opposed to file system level data. The advantage of using block level native protocol is reduced network-bandwidth requirement to transfer same amount of data as compared to file system level protocol. Our experiment and independent testing have shown that VCL servers allow much more number of concurrent users than existing products. For very high resolution DVD videos, VCL with 100Mbps NIC supports over 10 concurrent users viewing the same or different videos simultaneously. For VCD videos, the same VCL can support over 65 concurrent users viewing videos simultaneously. For data CDs, the VCL can support over 500 concurrent data stream users.

  19. Study on the urban heat island effect based on quantitative remote sensing technology

    NASA Astrophysics Data System (ADS)

    Nie, Yunju; Tong, Chengzhuo; Cheng, Penggen; Chen, Xiaoyong; Zhou, Mengyu

    2015-12-01

    In recent years, the effect of urban heat island (UHI) is increasingly obvious with moving forward in further urbanization process, which has become one of the prominent issues of environment. The image data of Nanchang city supplied by Landsat 5 Thematic Mapper (TM) in September 2006 is used in this paper, and the land surface temperature (LST) over the same period has been retrieved by using a mono-window algorithm based on remote sensing technology. The classification of LST is subsequently fulfilled by the method of proper density cutting. Characteristics of intensity and spatial distribution of UHI effect in Nanchang, as well as its relationships with land use type and vegetation coverage degree (VCD) are discussed in detail. The result shows that the phenomena of UHI are significantly presented in urban area with an inhomogeneous distribution, and the degree of influence of UHI depends on types of land uses. The intensity of UHI effect has a significant negative linear correlation with normalized difference vegetation index (NDVI). It is deduced that suitably optimizing land use types and raising VCR are obvious and effective ways to reduce UHI.

  20. Charmed and light pseudoscalar meson decay constants from HISQ simulations

    SciTech Connect

    Bazavov, Alexei; et al.

    2014-11-16

    We compute the leptonic decay constants $f_{D^+}$, $f_{D_s}$, and $f_{K^+}$, and the quark-mass ratios $m_c/m_s$ and $m_s/m_l$ in unquenched lattice QCD. We use the MILC highly improved staggered quark (HISQ) ensembles with four dynamical quark flavors. Our primary results are $f_{D^+} = 212.6(0.4)({}^{+1.0}_{-1.2})\\ \\mathrm{MeV}$, $f_{D_s} = 249.0(0.3)({}^{+1.1}_{-1.5})\\ \\mathrm{MeV}$, and $f_{D_s}/f_{D^+} = 1.1712(10)({}^{+29}_{-32})$, where the errors are statistical and total systematic, respectively. We also obtain $f_{K^+}/f_{\\pi^+} = 1.1956(10)({}^{+26}_{-18})$, updating our previous result, and determine the quark-mass ratios $m_s/m_l = 27.35(5)({}^{+10}_{-7})$ and $m_c/m_s = 11.747(19)({}^{+59}_{-43})$. When combined with experimental measurements of the decay rates, our results lead to precise determinations of the CKM matrix elements $|V_{us}| = 0.22487(51) (29)(20)(5)$, $|V_{cd}|=0.217(1) (5)(1)$ and $|V_{cs}|= 1.010(5)(18)(6)$, where the errors are from this calculation of the decay constants, the uncertainty in the experimental decay rates, structure-dependent electromagnetic corrections, and, in the case of $|V_{us}|$, the uncertainty in $|V_{ud}|$, respectively.

  1. Characterization of Highly Efficient CdTe Thin Film Solar Cells by Low-Temperature Photoluminescence

    NASA Astrophysics Data System (ADS)

    Okamoto, Tamotsu; Matsuzaki, Yuichi; Amin, Nowshad; Yamada, Akira; Konagai, Makoto

    1998-07-01

    Highly efficient CdTe thin film solar cells prepared by close-spaced sublimation (CSS) method with a glass/ITO/CdS/CdTe/Cu-doped carbon/Ag structure were characterized by low-temperature photoluminescence (PL) measurement. A broad 1.42 eV band probably due to VCd Cl defect complexes appeared as a result of CdCl2 treatment. CdS/CdTe junction PL revealed that a CdSxTe1-x mixed crystal layer was formed at the CdS/CdTe interface region during the deposition of CdTe by CSS and that CdCl2 treatment promoted the formation of the mixed crystal layer. Furthermore, in the PL spectra of the heat-treated CdTe after screen printing of the Cu-doped carbon electrode, a neutral-acceptor bound exciton (ACu0, X) line at 1.590 eV was observed, suggesting that Cu atoms were incorporated into CdTe as effective acceptors after the heat treatment.

  2. Features of quark and lepton mixing from differential geometry of curves on surfaces

    NASA Astrophysics Data System (ADS)

    Bordes, José; Hong-Mo, Chan; Pfaudler, Jakov; Sheung Tsun, Tsou

    1998-09-01

    It is noted that the Cabibbo-Kobayashi-Moskawa (CKM) matrix elements for both quarks and leptons as conceived in the dualized standard model (DSM) can be interpreted as direction cosines obtained by moving the Darboux trihedron (a 3-frame) along a trajectory on a sphere traced out through changing energy scales by a 3-vector factorized from the mass matrix. From the Darboux analogues of the well-known Serret-Frenet formulas for space curves, it is seen that the corner elements (Vub,Vtd for quarks, and Ue3,Uτ1 for leptons) are associated with the (geodesic) torsion, while the other off-diagonal elements (Vus,Vcd and Vcb,Vts for quarks, and Ue2,Uμ1 and Uμ3,Uτ2 for leptons) with the (respectively, geodesic and normal) curvatures of the trajectory. From this it follows that (i) the corner elements in both matrices are much smaller than the other elements, and (ii) the Uμ3,Uτ2 elements for the lepton CKM matrix are much larger than their counterparts in the quark matrix. Both these conclusions are strongly borne out by experiment, for quarks in hadron decays and for leptons in neutrino oscillations, and by previous explicit calculations within the DSM scheme.

  3. Cu-doped CdS and its application in CdTe thin film solar cell

    NASA Astrophysics Data System (ADS)

    Deng, Yi; Yang, Jun; Yang, Ruilong; Shen, Kai; Wang, Dezhao; Wang, Deliang

    2016-01-01

    Cu is widely used in the back contact formation of CdTe thin film solar cells. However, Cu is easily to diffuse from the back contact into the CdTe absorber layer and even to the cell junction interface CdS/CdTe. This phenomenon is generally believed to be the main factor affecting the CdTe solar cell stability. In this study Cu was intentionally doped in CdS thin film to study its effect on the microstructural, optical and electrical properties of the CdS material. Upon Cu doping, the VCd- and the surface-state-related photoluminescence emissions were dramatically decreased/quenched. The presence of Cu atom hindered the recrystallization/coalescence of the nano-sized grains in the as-deposited CdS film during the air and the CdCl2 annealing. CdTe thin film solar cell fabricated with Cu-doped CdS window layers demonstrated much decreased fill factor, which was induced by the increased space-charge recombination near the p-n junction and the worsened junction crystalline quality. Temperature dependent current-voltage curve measurement indicated that the doped Cu in the CdS window layer was not stable at both room and higher temperatures.

  4. Theoretical investigations into spectral and non-linear optical properties of brucine and strychnine using density functional theory.

    PubMed

    Islam, Nasarul; Niaz, Saba; Manzoor, Taniya; Pandith, Altaf Hussain

    2014-10-15

    The density functional theoretical (DFT) computations were performed at the B3LYP/6-311G++(d, p) level to calculate the equilibrium geometry, vibrational wave numbers, intensities, and various other molecular properties of brucine and strychnine, which were found in satisfactory agreement with the experimental data. The out-of-phase stretching modes of aromatic rings and carbonyl stretching modes in combination with CH stretching modes at stereogenic centers generate VCD signals, which are remarkably efficient configuration markers for these chiral molecular systems. NBOs analysis reveals that the large values of second order perturbation energy (47.24kcal/mol for brucine and 46.93kcal/mol for strychnine) confirms strong hyperconjugative interaction between the orbital containing the lone pair of electron of nitrogen and the neighboring CO antibonding orbital. The molecular electrostatic potential map of strychnine molecule, with no polar groups other than the lone keto group, shows less polarization, which accounts for its lower susceptibility towards electrophilic attack as compared to brucine.

  5. Effects of physical parameters on the cell-to-dendrite transition in directional solidification

    NASA Astrophysics Data System (ADS)

    Wei, Lei; Lin, Xin; Wang, Meng; Huang, Wei-Dong

    2015-07-01

    A quantitative cellular automaton model is used to study the cell-to-dendrite transition (CDT) in directional solidification. We give a detailed description of the CDT by carefully examining the influence of the physical parameters, including: the Gibbs-Thomson coefficient Γ, the solute diffusivity Dl, the solute partition coefficient k0, and the liquidus slope ml. It is found that most of the parameters agree with the Kurz and Fisher (KF) criterion, except for k0. The intrinsic relations among the critical velocity Vcd, the cellular primary spacing λc,max, and the critical spacing λcd are investigated. Project supported by the National Natural Science Foundation of China (Grant Nos. 51271213 and 51323008), the National Basic Research Program of China (Grant No. 2011CB610402), the National High Technology Research and Development Program of China (Grant No. 2013AA031103), the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20116102110016), and the China Postdoctoral Science Foundation (Grant No. 2013M540771).

  6. Stereochemical analysis of (+)-limonene using theoretical and experimental NMR and chiroptical data

    NASA Astrophysics Data System (ADS)

    Reinscheid, F.; Reinscheid, U. M.

    2016-02-01

    Using limonene as test molecule, the success and the limitations of three chiroptical methods (optical rotatory dispersion (ORD), electronic and vibrational circular dichroism, ECD and VCD) could be demonstrated. At quite low levels of theory (mpw1pw91/cc-pvdz, IEFPCM (integral equation formalism polarizable continuum model)) the experimental ORD values differ by less than 10 units from the calculated values. The modelling in the condensed phase still represents a challenge so that experimental NMR data were used to test for aggregation and solvent-solute interactions. After establishing a reasonable structural model, only the ECD spectra prediction showed a decisive dependence on the basis set: only augmented (in the case of Dunning's basis sets) or diffuse (in the case of Pople's basis sets) basis sets predicted the position and shape of the ECD bands correctly. Based on these result we propose a procedure to assign the absolute configuration (AC) of an unknown compound using the comparison between experimental and calculated chiroptical data.

  7. Development of an Exploration-Class Cascade Distillation System: Flight Like Prototype Design Status

    NASA Technical Reports Server (NTRS)

    Sargusingh, Miriam C.; Callahan, Michael R.

    2016-01-01

    The ability to recover and purify water through physiochemical processes is crucial for realizing long-term human space missions, including both planetary habitation and space travel. Because of their robust nature, distillation systems have been actively pursued as one of the technologies for water recovery. One such technology is the Cascade Distillation System (CDS) a multi-stage vacuum rotary distiller system designed to recover water in a microgravity environment. The CDS provides a similar function to the state of the art (SOA) vapor compressor distiller (VCD) currently employed on the International Space Station, but its control scheme and ancillary components are judged to be more straightforward and simpler to implement into a more reliable and efficient system. Through the Advanced Exploration Systems (AES) Life Support Systems (LSS) Project, the NASA Johnson Space Center (JSC) in collaboration with Honeywell International is developing a second generation flight forward prototype (CDS 2.0). A preliminary design fo the CDS 2.0 was presented to the project in September 2014. Following this review, detailed design of the system continued. The existing ground test prototype was used as a platform to demonstrate key 2.0 design and operational concepts to support this effort and mitigate design risk. A volumetric prototype was also developed to evaluate the packaging design for operability and maintainability. The updated system design was reviewed by the AES LSS Project and other key stakeholders in September 2015. This paper details the status of the CDS 2.0 design.

  8. Tropospheric Nitrogen Dioxide Column Density Trends Seen from the 10-year Record of OMI Measurements over East Asia

    NASA Astrophysics Data System (ADS)

    Irie, H.; Muto, T.; Itahashi, S.; Kurokawa, J. I.

    2015-12-01

    The Ozone Monitoring Instrument (OMI) aboard the Aura satellite recorded the 10-year (2005-2014) of tropospheric nitrogen dioxide (NO2) vertical column density (VCD) data. The data set taken over East Asia was analyzed to estimate linear trends on national and grid bases for two periods of 2005-2011 and 2011-2014. The most striking features are leveling-off or decreasing trends seen in NO2 VCDs over China for 2011-2014 after continuous increases for 2005-2011. In particular, a significant reduction by ~14% occurred from 2013 through 2014, attaining to the level of 2009. The grid-basis trend analysis implies that the turnaround seen in the trends occurred on a province or larger spatial scale and was likely due mainly to the technical improvement such as the widespread use of de-NOx units. Another prominent features are seen in Japan, where NO2 VCDs decreased at a rate of ~4% per year from 2005 to 2011. The rate was almost unchanged between the two periods 2005-2011 and 2011-2014, while the significant power substitution of thermal power generation for the nuclear power generation took place in Japan after 2011, when a massive earthquake occurred off the Pacific coast of northern Japan. This reflects a less contribution of NOx emissions from the power plant sector than that from the transport sector in the Pacific Belt Zone lying over metropolitan areas.

  9. Network Meta-analysis of Randomized Trials on the Safety of Vascular Closure Devices for Femoral Arterial Puncture Site Haemostasis.

    PubMed

    Jiang, Jun; Zou, Junjie; Ma, Hao; Jiao, Yuanyong; Yang, Hongyu; Zhang, Xiwei; Miao, Yi

    2015-09-08

    The safety of vascular closure devices (VCDs) is still debated. The emergence of more related randomized controlled trials (RCTs) and newer VCDs makes it necessary to further evaluate the safety of VCDs. Relevant RCTs were identified by searching PubMed, EMBASE, Google Scholar and the Cochrane Central Register of Controlled Trials electronic databases updated in December 2014. Traditional and network meta-analyses were conducted to evaluate the rate of combined adverse vascular events (CAVEs) and haematomas by calculating the risk ratios and 95% confidence intervals. Forty RCTs including 16868 patients were included. Traditional meta-analysis demonstrated that there was no significant difference in the rate of CAVEs between all the VCDs and manual compression (MC). Subgroup analysis showed that FemoSeal and VCDs reported after the year 2005 reduced CAVEs. Moreover, the use of VCDs reduced the risk of haematomas compared with MC. Network meta-analysis showed that AngioSeal, which might be the best VCD among all the included VCDs, was associated with reduced rates of both CAVE and haematomas compared with MC. In conclusion, the use of VCDs is associated with a decreased risk of haematomas, and FemoSeal and AngioSeal appears to be better than MC for reducing the rate of CAVEs.

  10. Optical property analysis of high-resistivity CZT:In single crystals before and after annealing

    NASA Astrophysics Data System (ADS)

    Yu, Pengfei; Jie, Wanqi

    2014-05-01

    In-doped CdZnTe:In (CZT:In) single crystals with high resistivity were annealed by an effective method containing Cd/Zn atmosphere annealing and Te atmosphere annealing. They were mainly measured by IR transmittance and Photoluminescence (PL) spectra. The results indicated Te inclusions were eliminated completely after annealing. Both of the resistivity and IR transmittance decreased notably after Cd/Zn atmosphere annealing, and then increased tremendously after Te atmosphere annealing. For PL measurements, (A0, X) disappeared, the intensity of (D0, X) peak increased, and FWHM was obviously reduced after annealing. These indicated the crystal quality was enhanced. The donor-acceptor pair peak decreased in annealed CZT:In crystal, which might be due to the dissociation of [VCd-InCd] complex and the remove of the impurities. Moreover, Dcomplex peak containing two peaks was caused by Cd vacancy-related (D1) and dislocation-related defects (D2) in as-grown crystal. However, after annealing, the intensities of D1 and D2 peaks decreased because of the compensation of Cd vacancies and the elimination of Te inclusions, respectively.

  11. Algorithm for NO2 Vertical Column Retrieval from the Ozone Monitoring Instrument

    NASA Technical Reports Server (NTRS)

    Bucsela, Eric J.; Celarier, Edward A.; Wenig, Mark O.; Gleason, James F.; Veefkind, J. Pepijn; Boersma, K. Folkert; Brinksma, Ellen J.

    2006-01-01

    We describe the operational algorithm for the retrieval of stratospheric, tropospheric, and total column densities of nitrogen dioxide NO2 from earthshine radiances measured by the Ozone Monitoring Instrument (OMI), aboard the EOS-Aura satellite. The algorithm uses the DOAS method for the retrieval of slant column NO densities. Air mass factors (AMFs) calculated from a stratospheric NO2 profile are used to make initial estimates of the vertical column density. Using data collected over a 24-h period, a smooth estimate of the global stratospheric field is constructed. Where the initial vertical column densities exceed the estimated stratospheric field, we infer the presence of tropospheric NO2, and recalculate the vertical column density (VCD) using an AMF calculated from an assumed tropospheric NO2 profile. The parameters that control the operational algorithm were selected with the aid of a set of data assembled from stratospheric and tropospheric chemical transport models. We apply the optimized algorithm to OMI data and present global maps of NO2 VCDs for the first time.

  12. First Global Maps of Stratospheric and Tropospheric NO2 from OMI

    NASA Technical Reports Server (NTRS)

    Bucsela, Eric J.; Celarier, Edward A.; Wenig, Mark O.; Gleason, James F.; Veefkind, J. Pepijn

    2004-01-01

    The Ozone Monitoring Instrument (OMI) was launched successfully in July 2004, as one of four instruments on the EOS Aura satellite. OMI makes hyperspectral measurements that are used to retrieve column densities of critical trace gases, including formaldehyde, BrO, SO2 and NO2 . We present the first results from the OM1 operational NO2 algorithm and demonstrate its ability to retrieve the tropospheric and stratospheric components of NO2. The DOAS method is used to determine slant column densities, and initial air mass factors (AMFs) are used. to give initial estimates of the vertical column densities (VCDs). VCDs from up to 15 consecutive orbits are collected, and a spatial filtering technique is applied to extract the synoptic-scale features characteristic of the stratospheric, field. features to be evidence of tropospheric excess NO2 , and apply an AMF appropriate to polluted conditions, to obtain an improved retrieval of the NO2 total VCD. We describe the assumptions underlying the algorithm in detail, and show global maps of NO2 VCDs, based on the first operational data from OMI.

  13. Spatial variance and assessment of nitrogen dioxide pollution in major cities of Pakistan along N5-Highway.

    PubMed

    Shabbir, Yasir; Khokhar, Muhammad Fahim; Shaiganfar, Reza; Wagner, Thomas

    2016-05-01

    This paper discusses the findings of the first car MAX-DOAS (multi-axis differential optical absorption spectroscopy) field campaign (300km long) along the National Highway-05 (N5-Highway) of Pakistan conducted on 13 and 14 November, 2012. The main objective of the field campaign was to assess the spatial distribution of tropospheric nitrogen dioxide (NO2) columns and corresponding concentrations along the N5-Highway from Islamabad to Lahore. Source identification of NO2 revealed that the concentrations were higher within major cities along the highway. The highest NO2 vertical column densities (NO2 VCDs) were found around two major cities of Rawalpindi and Lahore. This study also presents a comparison of NO2 VCDs measured by the ozone monitoring instrument (OMI) and car MAX-DOAS observations. The comparison revealed similar spatial distribution of the NO2 columns with both car MAX-DOAS and satellite observations, but the car MAX-DOAS observations show much more spatial details. Maximum NO2 VCD retrieved from car MAX-DOAS observations was up to an order of magnitude larger than the OMI observations in urban areas. PMID:27155404

  14. An overview of ISS ECLSS life testing at NASA, MSFC.

    PubMed

    Tatara, J D; Roman, M C

    1998-01-01

    Numerous components have been developed for use in the International Space Station (ISS) Environmental Control and Life Support System (ECLSS). Although these components have performed admirably for short-duration subsystem tests, there is little long-range operational (life test) data available. It is important to know not only how long a subsystem is anticipated to perform, but also the problems that can be expected should subsystem components fail. For this reason, the National Aeronautics and Space Administration (NASA) at the Marshall Space Flight Center (MSFC) developed the ECLSS Life Test program. To date, assemblies and subassemblies that are being or have been tested include the Trace Contaminant Control Subassembly (TCCS), the Vapor Compression Distillation Urine Processor Assembly (VCD-UPA), the Four-Bed Molecular Sieve Carbon Dioxide Removal Assembly (4BMS-CDRA), and the Solid Polymer Electrolyzer Oxygen Generation Assembly (SPE-OGA). Also included in life testing are noncomponent life test studies. These include the Water Degradation Study and the Biofilm Life Test. The Water Degradation Study looks at water quality changes after exposure to simulated ISS pre-Water Recovery Management (WRM) conditions. The Biofilm Life Test will examine microbial accumulation on surfaces in a simulated ISS water delivery system. This article will briefly review the objectives of each life test program, the results of completed tests, and the major problems observed during the tests.

  15. [Studies on the light-induced reversible xanthophyll-conversions in Chlorella and spinach leaves].

    PubMed

    Hager, A

    1967-06-01

    1. Using new methods in thin-layer chromatography, experiments were carried out to prove the light-induced changes in the quantity of various xanthophylls in Chlorella and spinach leaves. The probable connection of these interconversions to electron transport in photosynthesis was demonstrated. 2. The kinetics of these xanthophyll conversions were investigated during strong illumination and in the succeeding dark period (Chlorella). Already after illumination of 1 min one can detect a decrease of the di-epoxide xanthophyll violaxanthin and a corresponding increase of the epoxide-free zeaxanthin. The intermediate of this interconversion is the mono-epoxide antheraxanthin. Neoxanthin exhibits no change in concentration under the given light intensity and an illumination time of 60 min and more; the same result can be observed with the other carotenoids (α-carotene, β-carotene, lutein, lutein-5,6-epoxyd) and the chlorophylls a and b. 3. The light-induced formation of zeaxanthin is not correlated with those pigment interconversions which are photooxidative in their nature and which may be detected only after long illuminations. However, by using damaged, e.g., briefly heated Chlorella cells, a photooxidative-induced decrease of carotenes and chlorophyll a and a smaller decrease of xanthophylls and chlorophyll b could already be demonstrated after illumination of 15 min. In this case the ratio xanthophylls/ carotenes increases. 4. The transformation violaxanthin → antheraxanthin → zeaxanthin ("forward-reaction") is induced not only by an illumination with white light (point 2) but also with red light (>600 nm); that means the reaction proceeds at a wavelength which cannot be absorbed by the xanthophylls themselves. Chlorophyll acts as light-acceptor. 5. The "forward-reaction" does not proceed after the cells have been heated for a short time. The presence of inhibitors of light-reaction II in photosynthesis such as o-phenanthroline, hydroxylamine and DCMU entirely

  16. Development and application of a low-cost, portable DOAS system for stratospheric composition monitoring over the Argentinean Patagonia and Antarctic stations.

    NASA Astrophysics Data System (ADS)

    Raponi, Marcelo; Jiménez, Rodrigo; Ristori, Pablo; Wolfram, Elian; Tocho, Jorge; Quel, Eduardo

    2010-05-01

    A significant fraction of the Argentinean population is seasonally exposed to elevated UV radiation, particularly during severe stratospheric ozone destruction episodes in Antarctica. In order to provide early alert, global monitoring and to improve our understanding of these phenomena, various Argentinean and international organizations maintain stratospheric composition remote sensing sites from the southern tip of Argentina (Patagonia) to Antarctica. The understating of the ozone destruction dynamics will be significantly improved if more sites were available. For instance, the Laser and Applications Research Center, CEILAP (CITEFA-CONICET, Argentina) carries out systematic measurements of stratospheric ozone and tropospheric water vapor profiles at Rio Gallego (51° 36' S, 69° 19' W, 15 m asl) by means of LIDAR systems. Besides the active systems, the site possesses different passive instruments (GUV-541, UV-B and UV-A radiometers, SAOZ spectrometer, CIMEL sunphotometer) all of them working in synergy. The goal of this work is to present the design and development of a new compact atmospheric remote sensing system, able to determine the vertical column concentration in column (VCD) of multiple trace gases. We have developed a low-cost, portable passive DOAS system, ERO-DOAS, wich circumvents the cost limitations associated with new fixed monitoring sites. It is composed of commercial spectrophotometer (HR4000, Ocean Optics), a 400-μm core, 6-m long optic fiber, and a home-made automatic external shutter. We have developed a LabVIEW® based software for spectrometer/shutter control and data acquisition, and a MATLAB® based software for spectral data reduction. In the work we highlight the main characteristics of the system's components and we describe the visual interface implemented to controls the operation of the whole system, and the calculation algorithms to process the measured zenithal spectra, postulating the strategies implemented to solve the

  17. Aircraft measurements of bromine monoxide, iodine monoxide, and glyoxal profiles in the tropics: comparison with ship-based and in situ measurements

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Koenig, T. K.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-01-01

    increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° W). At 14.5 km 5-10 pptv NO2 agree with model predictions, and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF), and up to 500 m vertical resolution. The tropospheric BrO VCD was 1.5 × 1013 molec cm-2 (RF12), and at least 0.5 × 1013 molec cm-2 (RF17, 0-10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 × 1012 molec cm-2 (RF12) and 2.5 × 1012 molec cm-2 (RF17), and glyoxal VCDs of 2.6 × 1014 molec cm-2 (RF12) and 2.7 × 1014 molec cm-2 (RF17). Surprisingly, essentially all BrO, and the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1-0.2 pptv; glyoxal: 52 ± 5%, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere.

  18. Inorganic bromine and iodine in the TTL and in the mid-latitude lower stratosphere

    NASA Astrophysics Data System (ADS)

    Volkamer, Rainer; Apel, Eric; Atlas, Elliot; Bowdalo, Dene; Bresch, Jim; Dix, Barbara; Eloranta, Ed; Evans, Matthew; Gao, Ru-Shan; Jacob, Daniel; Kinnison, Doug; Koenig, Theodore; Lamarque, Jean-Francois; Morley, Bruce; Pierce, Brad; Saiz-Lopez, Alfonso; Salawitch, Ross; Schmidt, Johan; Wang, Siyuan

    2015-04-01

    Tropospheric chemistry of halogens (bromine and iodine) over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO) and iodine monoxide (IO) in the tropical troposphere. We present recent field measurements of BrO, IO, and their organic precursors that were conducted within the framework of the Tropical Ocean tRoposphere Exchange of Reactive halogen species and Oxygenated volatile organic compounds (TORERO, Jan/Feb 2012) over the tropical Eastern Pacific Ocean (tEPO). TORERO deployed an innovative payload of optical spectroscopic-, mass spectrometric-, and remote sensing instruments aboard the NSF/NCAR GV aircraft (HIAPER) with the objective to probe the composition of the TTL. BrO and IO were measured by the University of Colorado Airborne Multi AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, organic precursor gases by the Trace Organic Gas Analyzer (TOGA), and in situ aerosol size distributions by an Ultra High Sensitivity Aerosol Spectrometer (UHSAS); other parameters were also measured on the aircraft and used to constrain a photochemical box model to infer BrY. The measured BrO concentration strongly increased with altitude to 3.0 pptv BrO at 14.5 km (RF12, 9.1 to 8.6°N; 101.2 to 97.4°W). The average tropospheric BrO VCD in the tropics was 1.5 x1013 molec cm-2, which is in reasonable agreement with earlier satellite observations in the study area (~1.6 x1013 molec cm-2, Theys et al., 2011). However, the observed BrO VCD is 2-4 times higher than predictions from the GEOS-Chem model. Early results from the recent CONTRAST field campaign (CONvective TRansport of Active Species in the Tropics, Jan/Feb 2014) suggest lower tropospheric BrO over the Western Pacific Ocean (compared to the tEPO), but BrO is still higher than predicted by the CAM-Chem model. The largest model-measurement differences are observed in the

  19. Serum-Free Suspension Culture of MDCK Cells for Production of Influenza H1N1 Vaccines

    PubMed Central

    Huang, Ding; Peng, Wen-Juan; Ye, Qian; Liu, Xu-Ping; Zhao, Liang; Fan, Li; Xia-Hou, Kang; Jia, Han-Jing; Luo, Jian; Zhou, Lin-Ting; Li, Bei-Bei; Wang, Shi-Lei; Xu, Wen-Ting; Chen, Ze; Tan, Wen-Song

    2015-01-01

    Development of serum-free suspension cell culture processes is very important for influenza vaccine production. Previously, we developed a MDCK suspension cell line in a serum-free medium. In the present study, the growth kinetics of suspension MDCK cells and influenza virus production in the serum-free medium were investigated, in comparison with those of adherent MDCK cells in both serum-containing and serum-free medium. It was found that the serum-free medium supported the stable subculture and growth of both adherent and suspension cells. In batch culture, for both cell lines, the growth kinetics in the serum-free medium was comparable with those in the serum-containing medium and a commercialized serum-free medium. In the serum-free medium, peak viable cell density (VCD), haemagglutinin (HA) and median tissue culture infective dose (TCID50) titers of the two cell lines reached 4.51×106 cells/mL, 2.94Log10(HAU/50 μL) and 8.49Log10(virions/mL), and 5.97×106 cells/mL, 3.88Log10(HAU/50 μL), and 10.34Log10(virions/mL), respectively. While virus yield of adherent cells in the serum-free medium was similar to that in the serum-containing medium, suspension culture in the serum-free medium showed a higher virus yield than adherent cells in the serum-containing medium and suspension cells in the commercialized serum-free medium. However, the percentage of infectious viruses was lower for suspension culture in the serum-free medium. These results demonstrate the great potential of this suspension MDCK cell line in serum-free medium for influenza vaccine production and further improvements are warranted. PMID:26540170

  20. Adenomatous Polyposis Coli Mutation Leads to Myopia Development in Mice.

    PubMed

    Liu, Zhen; Qiu, Fangfang; Li, Jing; Zhu, Zhenzhen; Yang, Wenzhao; Zhou, Xiangtian; An, Jianhong; Huang, Furong; Wang, Qiongsi; Reinach, Peter S; Li, Wei; Chen, Wensheng; Liu, Zuguo

    2015-01-01

    Myopia incidence in China is rapidly becoming a very serious sight compromising problem in a large segment of the general population. Therefore, delineating the underlying mechanisms leading to myopia will markedly lessen the likelihood of other sight compromising complications. In this regard, there is some evidence that patients afflicted with familial adenomatous polyposis (FAP), havean adenomatous polyposis coli (APC) mutation and a higher incidence of myopia. To clarify this possible association, we determined whether the changes in pertinent biometric and biochemical parameters underlying postnatal refractive error development in APCMin mice are relevant for gaining insight into the pathogenesis of this disease in humans. The refraction and biometrics in APCMin mice and age-matched wild-type (WT) littermates between postnatal days P28 and P84 were examined with eccentric infrared photorefraction (EIR) and customized optical coherence tomography (OCT). Compared with WT littermates, the APCMin mutated mice developed myopia (average -4.64 D) on P84 which was associated with increased vitreous chamber depth (VCD). Furthermore, retinal and scleral changes appear in these mice along with: 1) axial length shortening; 2) increased retinal cell proliferation; 3) and decreased tyrosine hydroxylase (TH) expression, the rate-limiting enzyme of DA synthesis. Scleral collagen fibril diameters became heterogeneous and irregularly organized in the APCMin mice. Western blot analysis showed that scleral alpha-1 type I collagen (col1α1) expression also decreased whereas MMP2 and MMP9 mRNA expression was invariant. These results indicate that defective APC gene function promotes refractive error development. By characterizing in APCMin mice ocular developmental changes, this approach provides novel insight into underlying pathophysiological mechanisms contributing to human myopia development.

  1. FRESCO+: an improved O2 A-band cloud retrieval algorithm for tropospheric trace gas retrievals

    NASA Astrophysics Data System (ADS)

    Wang, P.; Stammes, P.; van der A, R.; Pinardi, G.; van Roozendael, M.

    2008-11-01

    The FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) algorithm has been used to retrieve cloud information from measurements of the O2 A-band around 760 nm by GOME, SCIAMACHY and GOME-2. The cloud parameters retrieved by FRESCO are the effective cloud fraction and cloud pressure, which are used for cloud correction in the retrieval of trace gases like O3 and NO2. To improve the cloud pressure retrieval for partly cloudy scenes, single Rayleigh scattering has been included in an improved version of the algorithm, called FRESCO+. We compared FRESCO+ and FRESCO effective cloud fractions and cloud pressures using simulated spectra and one month of GOME measured spectra. As expected, FRESCO+ gives more reliable cloud pressures over partly cloudy pixels. Simulations and comparisons with ground-based radar/lidar measurements of clouds show that the FRESCO+ cloud pressure is about the optical midlevel of the cloud. Globally averaged, the FRESCO+ cloud pressure is about 50 hPa higher than the FRESCO cloud pressure, while the FRESCO+ effective cloud fraction is about 0.01 larger. The effect of FRESCO+ cloud parameters on O3 and NO2 vertical column density (VCD) retrievals is studied using SCIAMACHY data and ground-based DOAS measurements. We find that the FRESCO+ algorithm has a significant effect on tropospheric NO2 retrievals but a minor effect on total O3 retrievals. The retrieved SCIAMACHY tropospheric NO2 VCDs using FRESCO+ cloud parameters (v1.1) are lower than the tropospheric NO2VCDs which used FRESCO cloud parameters (v1.04), in particular over heavily polluted areas with low clouds. The difference between SCIAMACHY tropospheric NO2 VCDs v1.1 and ground-based MAXDOAS measurements performed in Cabauw, The Netherlands, during the DANDELIONS campaign is about -2.12×1014molec cm-2.

  2. Limb-nadir matching using non-coincident NO2 observations: proof of concept and the OMI-minus-OSIRIS prototype product

    NASA Astrophysics Data System (ADS)

    Adams, Cristen; Normand, Elise N.; McLinden, Chris A.; Bourassa, Adam E.; Lloyd, Nicholas D.; Degenstein, Douglas A.; Krotkov, Nickolay A.; Belmonte Rivas, Maria; Folkert Boersma, K.; Eskes, Henk

    2016-08-01

    A variant of the limb-nadir matching technique for deriving tropospheric NO2 columns is presented in which the stratospheric component of the NO2 slant column density (SCD) measured by the Ozone Monitoring Instrument (OMI) is removed using non-coincident profiles from the Optical Spectrograph and InfraRed Imaging System (OSIRIS). In order to correct their mismatch in local time and the diurnal variation of stratospheric NO2, OSIRIS profiles, which were measured just after sunrise, were mapped to the local time of OMI observations using a photochemical box model. Following the profile time adjustment, OSIRIS NO2 stratospheric vertical column densities (VCDs) were calculated. For profiles that did not reach down to the tropopause, VCDs were adjusted using the photochemical model. Using air mass factors from the OMI Standard Product (SP), a new tropospheric NO2 VCD product - referred to as OMI-minus-OSIRIS (OmO) - was generated through limb-nadir matching. To accomplish this, the OMI total SCDs were scaled using correction factors derived from the next-generation SCDs that improve upon the spectral fitting used for the current operational products. One year, 2008, of OmO was generated for 60° S to 60° N and a cursory evaluation was performed. The OmO product was found to capture the main features of tropospheric NO2, including a background value of about 0.3 × 1015 molecules cm-2 over the tropical Pacific and values comparable to the OMI operational products over anthropogenic source areas. While additional study is required, these results suggest that a limb-nadir matching approach is feasible for the removal of stratospheric NO2 measured by a polar orbiter from a nadir-viewing instrument in a geostationary orbit such as Tropospheric Emissions: Monitoring of Pollution (TEMPO) or Sentinel-4.

  3. Temporal and spatial characteristics of lightning-produced nitrogen oxides in China

    NASA Astrophysics Data System (ADS)

    Fengxia, Guo; Min, Bao; Yijun, Mu; Zupei, Liu; Yawen, Li; Haifeng, Shi

    2016-11-01

    Tropospheric NO2 vertical column densities (NO2VCDs) retrieved from the Global Ozone Monitoring Experiment-2 satellite spectrometer, as well as lightning flashes measured by an Optical Transient Detector and Lightning Image Sensor from 1997 to 2013 are used to investigate spatial and temporal characteristics of lightning-produced nitrogen oxides (LNOX) under the recent period of rapid and locally-unbalanced economic development in China. Correlations between spatial distributions of lightning flashes and monthly mean tropospheric NO2VCDs were analyzed over this period. Mean production of LNOX per flash is 330 mol[N]/flash which was estimated using the correlation between lightning flashes and monthly mean tropospheric NO2VCD for the Tibetan Plateau. Using this correlation, the spatial and temporal characteristics of the ratio of LNOX to tropospheric NOX in China were determined. Results show that the ratio of LNOX to the tropospheric NOX is small in eastern regions, having a developed industrial sector and dense population, but relatively large in western regions, with a developing industrial sector and sparser population. The annual mean value of LNOX contributing to tropospheric NOX is 7.5% in China, which is lower than global averages (10-20%). The difference in interannual variability of LNOX production contributing to tropospheric NOX in different areas is distinct, ranging from high to low values for the Tibetan Plateau, Pearl River Delta, Yangtze River Delta and Beijing-Tianjin-Hebei regions, respectively. This indicates that lightning had a large influence on the column density of tropospheric NOX on the Tibetan Plateau, a region typically used as a sensitivity indicator for climate change. Lightning had less influence on atmospheric environments of the Pearl River Delta, Yangtze River Delta and Beijing-Tianjin-Hebei regions.

  4. Comparison of ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) and satellite DOAS measurements of NO2 distribution over Ulaanbaatar (Mongolia) during summer 2013

    NASA Astrophysics Data System (ADS)

    Böhnke, Sebastian; Behrendt, Thomas; Bruse, Michael; Meixner, Franz X.; Mamtimin, Buhalqem

    2014-05-01

    Cities are immense sources of air pollutants; however, emission inventories in many of them still are highly uncertain, particularly in developing countries. Ulaanbaatar is the most populous and polluted area in Mongolia. Tropospheric NO2 is proved to be harmful to both, the atmospheric environment and human health. It might be meaningful and important to observe pollutant concentrations in an area-integrated form (satellite observations) to create a sound data basis for air quality control measures. In our study, we preliminary present the results of both satellite and ground-based Differential Optical Absorption Spectroscopy (DOAS) measurements of vertical column densities (VCDs) of NO2 in Ulaanbaatar (urban area). As a ground validation tool, the MAX-DOAS measurements carried out in Ulaanbaatar (Mongolia) summer 2013 and are applied at 3 different sites in the west of Ulaanbaatar (106.73° E / 47.83° N), the city center (106.92° E / 47.92° N) and in the east (107.12° E / 47.87° N). Additionally, Automatic Weather Stations (AWS) have been set up and ozone was measured by UV absorption technique also at the 3 sites. Preliminary results show that the NO2 column densities increase during sunset and decrease after sunrise, which is most likely caused by a longer light path resulting from high solar zenith angles (SZA). The maximum DSCDs (Differential Slant Column Densities) are observed around sunset and sunrise (up to 10^17 molec cm-², mainly a measurement effect as stated above). The daily minima of the vertical column densities (VCD) appear in the morning and in the afternoon (DSCD ~2×10^15 molec cm-²) while, around noon, a second maximum can be observed (DSCD ~4×10^16 molec cm-²). Satellite data show mean VCDs of about 3×10^15 molec cm-² in July and a varying agreement with MAX-DOAS measurements.

  5. Global Free-tropospheric NO2 Abundances Derived Using a Cloud Slicing Technique from AURA OMI

    NASA Technical Reports Server (NTRS)

    Choi, S.; Joiner, J.; Choi, Y.; Duncan, B.N.; Vasilkov, A.; Krotkov, N.; Bucsela, E.J.

    2014-01-01

    We derive free-tropospheric NO2 volume mixing ratios (VMRs) by applying a cloud-slicing technique to data from the Ozone Monitoring Instrument (OMI) on the Aura satellite. In the cloud-slicing approach, the slope of the above-cloud NO2 column versus the cloud scene pressure is proportional to the NO2 VMR. In this work, we use a sample of nearby OMI pixel data from a single orbit for the linear fit. The OMI data include cloud scene pressures from the rotational-Raman algorithm and above-cloud NO2 vertical column density (VCD) (defined as the NO2 column from the cloud scene pressure to the top of the atmosphere) from a differential optical absorption spectroscopy (DOAS) algorithm. We compare OMI-derived NO2 VMRs with in situ aircraft profiles measured during the NASA Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in 2006. The agreement is generally within the estimated uncertainties when appropriate data screening is applied. We then derive a global seasonal climatology of free-tropospheric NO2 VMR in cloudy conditions. Enhanced NO2 in the free troposphere commonly appears near polluted urban locations where NO2 produced in the boundary layer may be transported vertically out of the boundary layer and then horizontally away from the source. Signatures of lightning NO2 are also shown throughout low and middle latitude regions in summer months. A profile analysis of our cloud-slicing data indicates signatures of lightning-generated NO2 in the upper troposphere. Comparison of the climatology with simulations from the global modeling initiative (GMI) for cloudy conditions (cloud optical depth less than10) shows similarities in the spatial patterns of continental pollution outflow. However, there are also some differences in the seasonal variation of free-tropospheric NO2 VMRs near highly populated regions and in areas affected by lightning-generated NOx.

  6. Phosphorylation effect on the GSSS peptide conformation in water: Infrared, vibrational circular dichroism, and circular dichroism experiments and comparisons with molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Lee, Kyung-Koo; Joo, Cheonik; Yang, Seongeun; Han, Hogyu; Cho, Minhaeng

    2007-06-01

    The phosphorylation effect on the small peptide conformation in water has not been clearly understood yet, despite the widely acknowledged notion that control of protein activity by phosphorylation works mainly by inducing conformational change. To elucidate the detailed mechanism, we performed infrared (IR) absorption and vibrational and electronic circular dichroism studies of both unphosphorylated and phosphorylated tetrapeptides, GSSS 1 and GSSpS 2. The solution structure of the tetrapeptide is found to be little dependent on the presence of the neutral or negatively charged phosphoryl group, and to be a mixture of extended structures including polyproline II (PII) and β-sheet conformations. The additional band at 1598cm-1 in the amide I IR spectrum of the phosphorylated peptide GSSpS at neutral pD appears to be clear spectroscopic evidence for direct intramolecular hydrogen-bonding interaction between the side chain dianionic phosphoryl group and the backbone amide proton. On the basis of amide I IR band analyses, the authors found that the probability of finding the phosphoryl group strongly H bonded to the backbone proton in GSSpS is about 43% at pD 7.0 and 37°C. Such a H-bonding interaction in GSSpS has the biological standard enthalpy and entropy of -15.1kJ /mol and -51.2J/Kmol, respectively. Comparisons between the experimentally measured IR and VCD spectra and the numerically simulated ones suggested that the currently available force field parameters need to be properly modified. The results in this paper may shed light on an unknown mechanism of controlling the peptide conformation by phosphorylation.

  7. Bortezomib-related neuropathy may mask CNS relapse in multiple myeloma: A call for diligence

    PubMed Central

    Abid, Muhammad Bilal; De Mel, Sanjay; Abid, Muhammad Abbas; Tan, Kong Bing; Chng, Wee Joo

    2016-01-01

    ABSTRACT Background: Neuropathy is a common adverse effect of bortezomib. Isolated central nervous system (CNS) relapse in MM remains exceedingly rare and carries a dismal prognosis. We present an unusual case of bortezomib related neuropathy masking a CNS relapse of MM. Case presentation: A 57-year-old female was diagnosed with standard-risk MM with clinical and cytogenetic features not typically associated with CNS involvement. She was treated with 4 cycles of bortezomib/cyclophosphamide/dexamethasone (VCD) and achieved a VGPR, after which she underwent an autologous stem cell transplant (ASCT) followed by bortezomib maintenance. Six months after ASCT she developed symptoms suggestive of peripheral neuropathy which was attributed to bortezomib. However the symptoms persisted despite discontinuation of bortezomib. Imaging and cerebrospinal fluid analysis subsequently confirmed a CNS relapse. Discussion: CNS involvement in MM (CNS-MM) is uncommon and is considered an aggressive disease. Recently published literature has reported biomarkers with prognostic potential. However, isolated CNS relapse is even less common; an event which carries a very poor prognosis. Given the heterogeneous neurologic manifestations associated with MM, clinical suspicion may be masked by confounding factors such as bortezomib-based therapy. The disease may further remain incognito if the patient does not exhibit any of the high risk features and biomarkers associated with CNS involvement. Conclusion: In the era of proteasome inhibitor (PtdIns)/immunomodulator (IMID)-based therapy for MM which carries neurologic adverse effects, it is prudent to consider CNS relapse early. This case further highlights the need for more robust biomarkers to predict CNS relapse and use of newer novel agents which demonstrate potential for CNS penetration. PMID:27105248

  8. Adenomatous Polyposis Coli Mutation Leads to Myopia Development in Mice

    PubMed Central

    Li, Jing; Zhu, Zhenzhen; Yang, Wenzhao; Zhou, Xiangtian; An, Jianhong; Huang, Furong; Wang, Qiongsi; Reinach, Peter S.; Li, Wei; Chen, Wensheng; Liu, Zuguo

    2015-01-01

    Myopia incidence in China is rapidly becoming a very serious sight compromising problem in a large segment of the general population. Therefore, delineating the underlying mechanisms leading to myopia will markedly lessen the likelihood of other sight compromising complications. In this regard, there is some evidence that patients afflicted with familial adenomatous polyposis (FAP), havean adenomatous polyposis coli (APC) mutation and a higher incidence of myopia. To clarify this possible association, we determined whether the changes in pertinent biometric and biochemical parameters underlying postnatal refractive error development in APCMin mice are relevant for gaining insight into the pathogenesis of this disease in humans. The refraction and biometrics in APCMin mice and age-matched wild-type (WT) littermates between postnatal days P28 and P84 were examined with eccentric infrared photorefraction (EIR) and customized optical coherence tomography (OCT). Compared with WT littermates, the APCMin mutated mice developed myopia (average -4.64 D) on P84 which was associated with increased vitreous chamber depth (VCD). Furthermore, retinal and scleral changes appear in these mice along with: 1) axial length shortening; 2) increased retinal cell proliferation; 3) and decreased tyrosine hydroxylase (TH) expression, the rate-limiting enzyme of DA synthesis. Scleral collagen fibril diameters became heterogeneous and irregularly organized in the APCMin mice. Western blot analysis showed that scleral alpha-1 type I collagen (col1α1) expression also decreased whereas MMP2 and MMP9 mRNA expression was invariant. These results indicate that defective APC gene function promotes refractive error development. By characterizing in APCMin mice ocular developmental changes, this approach provides novel insight into underlying pathophysiological mechanisms contributing to human myopia development. PMID:26495845

  9. Estimation of NOx emissions from the Megacity of Lahore, Pakistan using car MAX-DOAS observations and comparison with OMI satellite data

    NASA Astrophysics Data System (ADS)

    Razi, Maria; Shaiganfar, Reza; Fahim Khokhar, Muhammad; Dörner, Steffen; Ahmad, Noor; Donner, Sebastian; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Lahore is a metropolitan city of Pakistan with about more than 10 million inhabitants and thus a strong emission source of atmospheric pollutants. The quantification of these emission sources is usually accomplished by so-called bottom-up inventories, based on the summation of the emissions of individual emission sources for all relevant emission categories. Such inventories are subject to large errors because of uncertainties in the emission estimates for individual sources as well as their numbers and characteristics. Here we present results of a top-down emission inventory for Lahore based on car multi-axis differential optical absorption spectroscopy (car-MAX-DOAS) observations. We performed such measurements around the city on Lahore on six days in December 2015. From the measured spectra we derive the vertically integrated concentration of NO2 along the driving route (the so called tropospheric vertical column density, VCD). By combining these observations with wind data we estimate the total NO2 emissions from the city of Lahore. Since from the measured spectra only NO2 (but not NO) can be retrieved, we convert the NO2 emissions to total NOx (NO2 plus NO) emissions. We also apply corrections for the decay of NOx on the way between the emission source and the location of the measurements. We compare the derived NOx emissions to existing emission inventories. We also compare the spatial distributions of the tropospheric NO2 VCDs observed by car MAX-DOAS with collocated results from satellite observations of the Ozone Monitoring Instrument (OMI).

  10. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-01

    Laser spectroscopy is a powerful tool for analyzing small molecules, i.e. in the gas phase. In the mid-infrared spectral region quantum cascade lasers (QCLs) have been established as the most frequently used laser radiation source. Spectroscopy of larger molecules in the gas phase, of complex mixtures, and analysis in the liquid phase requires a broader tuning range and is thus still the domain of Fourier transform infrared (FTIR) spectroscopy. However, the development of tunable external cavity (EC) QCLs is starting to change this situation. The main advantage of QCLs is their high spectral emission power that is enhanced by a factor of 10(4) compared with thermal light sources. Obviously, transmission measurements with EC-QCLs in strongly absorbing samples are feasible, which can hardly be measured by FTIR due to detector noise limitations. We show that the high power of EC-QCLs facilitates spectroscopy beyond simple absorption measurements. Starting from QCL experiments with liquid samples, we show results of fiber evanescent field analysis (FEFA) to detect pesticides in drinking water. FEFA is a special case of attenuated total reflection spectroscopy. Furthermore, powerful CW EC-QCLs enable fast vibrational circular dichroism (VCD) spectroscopy of chiral molecules in the liquid phase - a technique which is very time consuming with standard FTIR equipment. We present results obtained for the chiral compound 1,1'-bi-2-naphthol (BINOL). Finally, powerful CW EC-QCLs enable the application of laser photothermal emission spectroscopy (LPTES). We demonstrate this for a narrowband and broadband absorber in the gas phase. All three techniques have great potential for MIR process analytical applications.

  11. Major soluble proteome changes in Deinococcus deserti over the earliest stages following gamma-ray irradiation

    PubMed Central

    2013-01-01

    Background Deinococcus deserti VCD115 has been isolated from Sahara surface sand. This radiotolerant bacterium represents an experimental model of choice to understand adaptation to harsh conditions encountered in hot arid deserts. We analysed the soluble proteome dynamics in this environmentally relevant model after exposure to 3 kGy gamma radiation, a non-lethal dose that generates massive DNA damages. For this, cells were harvested at different time lapses after irradiation and their soluble proteome contents have been analysed by 2-DE and mass spectrometry. Results In the first stage of the time course we observed accumulation of DNA damage response protein DdrB (that shows the highest fold change ~11), SSB, and two different RecA proteins (RecAP and RecAC). Induction of DNA repair protein PprA, DNA damage response protein DdrD and the two gyrase subunits (GyrA and GyrB) was also detected. A response regulator of the SarP family, a type II site-specific deoxyribonuclease and a putative N-acetyltransferase are three new proteins found to be induced. In a more delayed stage, we observed accumulation of several proteins related to central metabolism and protein turn-over, as well as helicase UvrD and novel forms of both gyrase subunits differing in terms of isoelectric point and molecular weight. Conclusions Post-translational modifications of GyrA (N-terminal methionine removal and acetylation) have been evidenced and their significance discussed. We found that the Deide_02842 restriction enzyme, which is specifically found in D. deserti, is a new potential member of the radiation/desiccation response regulon, highlighting the specificities of D. deserti compared to the D. radiodurans model. PMID:23320389

  12. Data series of total columns of H2O measured from the ground and from space at Observatoire de Haute-Provence in France (44° N)

    NASA Astrophysics Data System (ADS)

    Alkasm, Sulaf; Sarkissian, Alain; Keckhut, Philippe; Pazmino, Andrea; Goutail, Florence; Noel, Stephan

    2013-04-01

    Water vapour is an atmospheric constituent having a determinant effect on the climate and on the weather. It presents the two third of the greenhouse gases, and is mostly located in the troposphere. It is the key element of the hydrological cycle, conditioned by exchanges between its three phases in the atmosphere, the ocean and the continents, and also directed by the transport of energy between the surface and the atmosphere, by evaporation and condensation. However, because of its large temporal and spatial variability, the measure of this component is a demanding task. For this reason, many different techniques have been developed to estimate water vapour in the atmosphere. Also, the accuracy of the measurements changes from one instrument to another as the mode of observation, the period of observation, the condition of measurement, and the retrieval method are different between them. Note that these instruments were not specialised initially to water vapour measurements and the extraction of H2O was not the principle objective. This paper compares measurements of total vertical column density (VCD) of water vapour, i.e. the amount of water vapour in a vertical atmospheric column, obtained above Observatoire de Haute-Provence (OHP), south of France (5°42'E, +43°55'N) from five different instruments. This work compares results from two ground based and three satellite instruments: the SAOZ (système d'analyse par observation zénithale) an automated UV-VIS spectrometer; Elodie, a cross-dispersed echelle spectrograph and its 1.92 m telescope; SCIAMACHY, a scanning imaging absorption spectrometer for atmospheric cartography; GOME, a nadir scanning ultraviolet and visible spectrometer for global monitoring of atmospheric ozone; and GOME2, a second generation of GOME.

  13. FRESCO+: an improved O2 A-band cloud retrieval algorithm for tropospheric trace gas retrievals

    NASA Astrophysics Data System (ADS)

    Wang, P.; Stammes, P.; van der A, R.; Pinardi, G.; van Roozendael, M.

    2008-05-01

    The FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) algorithm has been used to retrieve cloud information from measurements of the O2 A-band around 760 nm by GOME, SCIAMACHY and GOME-2. The cloud parameters retrieved by FRESCO are the effective cloud fraction and cloud pressure, which are used for cloud correction in the retrieval of trace gases like O3 and NO2. To improve the cloud pressure retrieval for partly cloudy scenes, single Rayleigh scattering has been included in an improved version of the algorithm, called FRESCO+. We compared FRESCO+ and FRESCO effective cloud fractions and cloud pressures using simulated spectra and one month of GOME measured spectra. As expected, FRESCO+ gives more reliable cloud pressures over partly cloudy pixels. Simulations and comparisons with ground-based radar/lidar measurements of clouds shows that the FRESCO+ cloud pressure is about the optical midlevel of the cloud. Globally averaged, the FRESCO+ cloud pressure is about 50 hPa higher than the FRESCO cloud pressure, while the FRESCO+ effective cloud fraction is about 0.01 larger. The effect of FRESCO+ cloud parameters on O3 and NO2 vertical column densities (VCD) is studied using SCIAMACHY data and ground-based DOAS measurements. We find that the FRESCO+ algorithm has a significant effect on tropospheric NO2 retrievals but a minor effect on total O3 retrievals. The retrieved SCIAMACHY tropospheric NO2 VCDs using FRESCO+ cloud parameters (v1.1) are lower than the tropospheric NO2 VCDs which used FRESCO cloud parameters (v1.04), in particular over heavily polluted areas with low clouds. The difference between SCIAMACHY tropospheric NO2 VCDs v1.1 and ground-based MAXDOAS measurements performed in Cabauw, The Netherlands, during the DANDELIONS campaign is about -2.12×1014 molec cm-2.

  14. Inter-comparison of MAX-DOAS Retrieved Vertical Profiles of Aerosol Extinction, SO2 and NO2 in the Alberta Oil Sands with LIDAR Data and GEM-MACH Air Quality Model.

    NASA Astrophysics Data System (ADS)

    Davis, Zoe; Friess, Udo; Strawbridge, Kevin; Whiteway, James; Aggarwal, Monika; Makar, Paul; Li, Shao-Meng; O'Brien, Jason; Baray, Sabour; Schnitzler, Elijah; Olfert, Jason S.; Osthoff, Hans D.; Lobo, Akshay; McLaren, Robert

    2016-04-01

    Understanding industrial emissions of trace gas pollutants in the Alberta oil sands is essential to maintaining air quality standards and informing public policy. Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of trace gases can improve knowledge of pollutant levels, vertical distribution and chemical transformation. During an intensive air measurement campaign to study emissions, transport, transformation and deposition of oil sands air pollutants from August to September of 2013, a MAX-DOAS instrument was deployed at a site north of Fort McMurray, Alberta to determine the vertical profiles of aerosol extinction, NO2 and SO2 through retrieval from the MAX-DOAS spectral measurements using an optimal estimation method. The large complement of data collected from multiple instruments deployed during this field campaign provides a unique opportunity to validate and characterize the performance of the MAX-DOAS vertical profile retrievals. Aerosol extinction profiles determined from two Light Detection and Ranging (LIDAR) instruments, one collocated and the other on a Twin Otter aircraft that flew over the site during the study, will be compared to the MAX-DOAS aerosol extinction profile retrievals. Vertical profiles of NO2 and SO2 retrieved from the MAX-DOAS measurements will be further compared with the composite vertical profiles measured from the flights of a second aircraft, the NRC-Convair 580, over the field site during the same measurement period. Finally, the MAX-DOAS retrieved tropospheric vertical column densities (VCDs) of SO2 and NO2 will be compared to the predicted VCDs from Environment and Climate Change Canada's Global Environmental Multi-scale - Modelling Air quality and Chemistry (GEM-MACH) air quality model over the grid cell containing the field site. Emission estimates of SO2 from the major oil mining facility Syncrude Mildred Lake using the MAX-DOAS VCD results, validated through the detailed characterization above

  15. Nearest Neighbor Interactions Affect the Conformational Distribution in the Unfolded State of Peptides

    NASA Astrophysics Data System (ADS)

    Toal, Siobhan; Schweitzer-Stenner, Reinhard; Rybka, Karin; Schwalbe, Hardol

    2013-03-01

    In order to enable structural predictions of intrinsically disordered proteins (IDPs) the intrinsic conformational propensities of amino acids must be complimented by information on nearest-neighbor interactions. To explore the influence of nearest-neighbors on conformational distributions, we preformed a joint vibrational (Infrared, Vibrational Circular Dichroism (VCD), polarized Raman) and 2D-NMR study of selected GxyG host-guest peptides: GDyG, GSyG, GxLG, GxVG, where x/y ={A,K,LV}. D and S (L and V) were chosen at the x (y) position due to their observance to drastically change the distribution of alanine in xAy tripeptide sequences in truncated coil libraries. The conformationally sensitive amide' profiles of the respective spectra were analyzed in terms of a statistical ensemble described as a superposition of 2D-Gaussian functions in Ramachandran space representing sub-ensembles of pPII-, β-strand-, helical-, and turn-like conformations. Our analysis and simulation of the amide I' band profiles exploits excitonic coupling between the local amide I' vibrational modes in the tetra-peptides. The resulting distributions reveal that D and S, which themselves have high propensities for turn-structures, strongly affect the conformational distribution of their downstream neighbor. Taken together, our results indicate that Dx and Sx motifs might act as conformational randomizers in proteins, attenuating intrinsic propensities of neighboring residues. Overall, our results show that nearest neighbor interactions contribute significantly to the Gibbs energy landscape of disordered peptides and proteins.

  16. Chemometrics and in-line near infrared spectroscopic monitoring of a biopharmaceutical Chinese hamster ovary cell culture: prediction of multiple cultivation variables.

    PubMed

    Clavaud, Matthieu; Roggo, Yves; Von Daeniken, Ralph; Liebler, André; Schwabe, Jan-Oliver

    2013-07-15

    In the present study near infrared (NIR) spectroscopy was used to monitor the cultivation of mammalian Chinese hamster ovary (CHO) cells producing a monoclonal antibody in a fed-batch cell culture process. A temperature shift was applied during the cultivation. The cells were incubated at 37 °C and 33 °C. The Fourier transform near infrared (FT-NIR) multiplex process analyzer spectroscopy was investigated to monitor cultivation variables of the CHO cell culture from 10 independent batches using two channels of the FT-NIR. The measurements were performed on production scale bioreactors of 12,500 L. The cell cultures were analyzed with the spectrometer coupled to a transflection sterilizable fiber optic probe inserted into the bioreactors. Multivariate data analysis (MVDA) employing unsupervised principal component analysis (PCA) and partial least squares regression methods (PLS) were applied. PCA demonstrated that 96% of the observed variability was explained by the process trajectory and the inter-batch variability. PCA was found to be a significant tool in identifying batch homogeneity between lots and in detecting abnormal fermentation runs. Seven different cell culture parameters such as osmolality, glucose concentration, product titer, packed cell volume (PCV), integrated viable packed cell volume (ivPCV), viable cell density (VCD), and integrated viable cell count (iVCC) were monitored inline and predicted by NIR. NIR spectra and reference analytics data were computed using control charts to evaluate the monitoring abilities. Control charts of each media component were under control by NIR spectroscopy. The PLS calibration plots offered accurate predictive capabilities for each media. This paper underlines the capability for inline prediction of multiple cultivation variables during bioprocess monitoring.

  17. Improved Satellite Retrievals of NO2 and SO2 over the Canadian Oil Sands and Comparisons with Surface Measurements

    NASA Technical Reports Server (NTRS)

    McLinden, C. A.; Fioletov, V.; Boersma, K. F.; Kharol, S. K.; Krotkov, N.; Lamsal, L.; Makar, P. A.; Martin, R. V.; Veefkind, J. P.; Yang, K.

    2014-01-01

    Satellite remote sensing is increasingly being used to monitor air quality over localized sources such as the Canadian oil sands. Following an initial study, significantly low biases have been identified in current NO2 and SO2 retrieval products from the Ozone Monitoring Instrument (OMI) satellite sensor over this location resulting from a combination of its rapid development and small spatial scale. Air mass factors (AMFs) used to convert line-of-sight "slant" columns to vertical columns were re-calculated for this region based on updated and higher resolution input information including absorber profiles from a regional-scale (15 km × 15 km resolution) air quality model, higher spatial and temporal resolution surface reflectivity, and an improved treatment of snow. The overall impact of these new Environment Canada (EC) AMFs led to substantial increases in the peak NO2 and SO2 average vertical column density (VCD), occurring over an area of intensive surface mining, by factors of 2 and 1.4, respectively, relative to estimates made with previous AMFs. Comparisons are made with long-term averages of NO2 and SO2 (2005-2011) from in situ surface monitors by using the air quality model to map the OMI VCDs to surface concentrations. This new OMI-EC product is able to capture the spatial distribution of the in situ instruments (slopes of 0.65 to 1.0, correlation coefficients of greater than 0.9). The concentration absolute values from surface network observations were in reasonable agreement, with OMI-EC NO2 and SO2 biased low by roughly 30%. Several complications were addressed including correction for the interference effect in the surface NO2 instruments and smoothing and clear-sky biases in the OMI measurements. Overall these results highlight the importance of using input information that accounts for the spatial and temporal variability of the location of interest when performing retrievals.

  18. Overexpression of Serpinb1 in Chinese hamster ovary cells increases recombinant IgG productivity.

    PubMed

    Lin, Nan; Brooks, Jeanne; Sealover, Natalie; George, Henry J; Kayser, Kevin J

    2015-01-10

    We report the discovery and validation of a novel CHO cell engineering target for improving IgG expression, serpin peptidase inhibitor, clade B, member 1 (Serpinb1). Transcriptomic studies using microarrays revealed that Serpinb1 was up-regulated in cultures with IgG heavy and light chain transcription transiently repressed compared with cultures treated with non-targeting siRNA. As proof of concept, a lentiviral vector was employed to overexpress the Chinese Hamster Serpinb1 in a CHOZN(®) Glutamine Synthetase (-/-) recombinant IgG producing CHO line. The lentiviral stable pool demonstrated 4.2-fold SERPINB1 overexpression compared with the non-transduced control. The peak viable cell density (VCD) and peak IgG volumetric productivity of the lentiviral stable pool increased 1.3 and 2.0 fold, respectively, compared with the non-transduced control. For host cell engineering, a plasmid encoding SERPINB1 was transfected into the CHOZN(®) GS (-/-) host cell line to create several stable pools. Single-cell clones isolated from the pools were characterized for their SERPINB1 expression levels and growth. The clone (SERPINB1_OE_27) with the highest SERPINB1 expression had decreased peak viable cell density and exponential phase growth rate. Selected SERPINB1 OE clones were subsequently evaluated for their IgG expression capabilities using GS selection. Clone SERPINB1_OE_42 with moderate SERPINB1 overexpression demonstrated increased IgG productivity in "bulk" selection. We conclude that manipulating Serpinb1 expression can lead to increased recombinant IgG productivity, but the effect in host cell lines may vary by clone and by overexpression level. This work represents the ongoing effort in applying "-omics" findings to novel CHO host cell line engineering.

  19. Accelerating the Adoption of Second-Tier Reach Standards forApplicable Appliance Products in China

    SciTech Connect

    Lin, Jiang; Fridley, David

    2007-03-01

    The minimum energy efficiency standards program for household appliances in China was initiated in 1989. Since 1996, CLASP and its implementing partner, LBNL, have assisted China in developing 11 minimum energy performance standards (MEPS) for 9 products and endorsement labels for 11 products including: refrigerators; air conditioners; clothes washers; televisions; printers; computers; monitors; fax machines; copiers; DVD/VCD players; external power supplies; and set-top boxes (under development). Before 2003, China's traditional approach to standards development involved small increases in efficiency requirements for implementation within 6 months of a standard's approval. Since 2003, China has adopted a new approach in setting MEPS. This new approach involves the development of two tiers of standards--one for initial implementation and a second tier at a more aggressive level of energy efficiency for implementation three to five years later. The second-tier standard is also referred to as a 'reach standard'. Reach standards have now been developed in China for: color TVs; refrigerators; air conditioners; and external power supplies. This report is presented in five sections. After the introduction in Section 1, Section 2 analyzes the distribution of the efficiency of refrigerators and air-conditioners in China based on data collected by the China Energy Label Center for the mandatory energy information label program. The results provide an assessment of the adoption of reach standards for these two products. Section 3 summarizes on-going collaborations with Shanghai related to early local adoption of reach standards, and presents both the impact and an analysis of barriers to the local adoption of reach standard for air-conditioners. Section 4 offers suggestions for local governments on how to move forward in adopting reach standards in their localities and concludes with a summary of the results and a plan for developing local capacity in order to achieve

  20. Conformational manifold of alpha-aminoisobutyric acid (Aib) containing alanine-based tripeptides in aqueous solution explored by vibrational spectroscopy, electronic circular dichroism spectroscopy, and molecular dynamics simulations.

    PubMed

    Schweitzer-Stenner, Reinhard; Gonzales, Widalys; Bourne, Gregory T; Feng, Jianwen A; Marshall, Garland R

    2007-10-31

    Replacement of the alpha-proton of an alanine residue to generate alpha-aminoisobutyric acid (Aib) in alanine-based oligopeptides favors the formation of a 3(10) helix when the length of the oligopeptide is about four to six residues. This research was aimed at experimentally identifying the structural impact of an individual Aib residue in an alanine context of short peptides in water and Aib's influence on the conformation of nearest-neighbor residues. The amide I band profile of the IR, isotropic and anisotropic Raman, and vibrational circular dichroism (VCD) spectra of Ac-Ala-Ala-Aib-OMe, Ac-Ala-Aib-Ala-OMe, and Ac-Aib-Ala-Ala-OMe were measured and analyzed in terms of different structural models by utilizing an algorithm that exploits the excitonic coupling between amide I' modes. The conformational search was guided by the respective 1H NMR and electronic circular dichroism spectra of the respective peptides, which were also recorded. From these analyses, all peptides adopted multiple conformations. Aib predominantly sampled the right-handed and left-handed 3(10)-helix region and to a minor extent the bridge region between the polyproline (PPII) and the helical regions of the Ramachandran plot. Generally, alanine showed the anticipated PPII propensity, but its conformational equilibrium was shifted towards helical conformations in Ac-Aib-Ala-Ala-OMe, indicating that Aib can induce helical conformations of neighboring residues positioned towards the C-terminal direction of the peptide. An energy landscape exploration by molecular dynamics simulations corroborated the results of the spectroscopic studies. They also revealed the dynamics and pathways of potential conformational transitions of the corresponding Aib residues.

  1. Total Column NO2 from the OMI Instrument on EOS Aura

    NASA Astrophysics Data System (ADS)

    Brinksma, E. J.; Boersma, K. F.; Gleason, J. F.; Bucsela, E. J.; Celarier, E.; de Haan, J. F.; Veefkind, J. P.

    2003-04-01

    OMI-EOS is a Dutch-Finnish nadir pointing spaceborne imaging spectrometer that will fly on NASA's Aura Mission, which is part of the Earth Observation System (EOS). OMI measures the reflected solar radiation in the ultraviolet and visible spectrum between 270 and 500 nm, using two channels with a spectral resolution of about 0.5 nm. OMI data products include ozone columns and profiles, aerosols, clouds, surface UV irradiance, and the trace gases NO_2, SO_2, HCHO, BrO, and OClO. Total column NO_2 will be measured using data from the visible channel, range, 365 - 500 nm; resolution, 0.63 nm; sampling, 0.21 nm/pixel. The NO_2 algorithm will compute vertical column densities (VCD) from spectrally fitted NO_2 slant column densities (SCD). The method to determine NO_2 slant column densities is Differential Optical Absorption Spectroscopy (DOAS), which uses a linear decomposition of a measured Earth reflectance spectrum into its component spectra, including NO_2, O_3, O_2-O_2, H_2O, Ring and a third order polynomial. Calculation of the air mass factor in regions of enhanced tropospheric NO_2 will be accomplished by designating two components of the column density: an unpolluted component, which includes stratospheric and free tropospheric NO_2, and a polluted component, containing boundary layer NO_2. The two parts will be separated through spatial filtering of the geographic NO_2 field. Polluted NO_2 is assumed to show the greatest small-scale variation and will be isolated and corrected for air mass factor and temperature.

  2. Deep level study of cadmium sulfide/cadmium telluride solar cells

    NASA Astrophysics Data System (ADS)

    Komin, Valery Vitalyevich

    The goal of this project is to develop a reliable approach to characterize defects in CdTe/CdS solar cells, taking into account the requirements dictated by the polycrystallinity of the device materials, to characterize solar cells prepared in different processing conditions, to develop an understanding on how processing variations correlate with changes in the overall device performance and stability, and to develop recommendations on the optimization of processing conditions based on this analysis. Polycrystalline CdTe/CdS solar cells were studied using double boxcar deep level transient spectroscopy (DLTS) and correlation DLTS measurements to investigate the effect of the post-growth CdCl2 heat treatment, and the effect of the HgTe:Cu-doped graphite and Ni2P-based back contacts. The limitations of each deep-level characterization technique dictated by the polycrystalline nature of the CdTe/CdS heterostructure, were taken in consideration. Dark C-V, dark and illuminated J-V measurements were performed in order to monitor changes in the solar cell parameters during the deep level studies. To avoid issues associated with the metastability of some defects, all experiments were performed in the dark. Twelve traps were detected in the temperature range from 90K to 360K. Preliminary solar cell simulations using AMPS-1D were used to help understand the role of these traps in the current transport mechanism and the impact of their presence on the overall device performance. A donor-like defect with activation energy EA = 0.140 eV was identified as a chlorine-related DX2-state of (VCd2--ClTe+) complex. Its presence in the CdTe layer was associated with significant degradation of overall solar cell performance. An acceptor-like defect with activation energy EA = 0.350 was identified as a defect Cu Cd- or complex (Cui+-2Cu Cd-)-. Recommendations for processing condition optimization are made based on the results of this study.

  3. Photoluminescence study of copper-doped cadmium-telluride and related stability issues for cadmium-sulfide/cadmium-telluride solar-cell devices

    NASA Astrophysics Data System (ADS)

    Grecu, Dan S.

    Lifetime predictions for CdTe photovoltaic modules represent a complex problem, partly due to the fact that a fundamental understanding of the CdTe material properties and device operation is far from being complete. One of the stability issues actively investigated is the use of Cu for the formation of a back contact. Cu is one of the few good p-dopants for CdTe, which, by forming a p+ layer at the surface of the CdTe, relaxes the requirement for a high work function metal at the back contact. On the other hand, it is known that Cu is a fast diffuser in CdTe and it was suggested that Cu migration within the device could lead to some of the observed degradation effects. in this work, we explore Cu states and migration effects in CdTe and CdS/CdTe devices using photoluminescence (PL) as the main investigative method. We confirm the assignment of several Cu-related PL transitions observed in the CdTe spectrum, namely, a bound exciton transition (X, CUCd) at 1.59eV and a donor-acceptor pair (DAP) (D, CuCd) at 1.45eV. In addition, we observe and characterize new effects related to Cu diffusion in CdTe: (a) the quenching of a DAP, Cd-vacancy related band, at 1.55eV, and (b) the formation of a new strong lattice-coupled transition at 1.555eV. These effects, we suggest, are consistent with Cu atoms occupying substitutional positions on the Cd sublattice and/or forming Frenkel pairs of the type CUi-VCd- with Cd vacancies. Similar spectral characteristics are observed for the low-S-content CdS-CdTe alloy existent in the vicinity of the junction in solar-cell devices. Using Cu-induced changes in the PL spectrum, we propose that Cu diffuses rapidly through an interstitial mechanism, as a positively charged ion, throughout the CdTe and possibly the CdS layer during the back-contact fabrication procedure. Applied electrical fields can reverse the direction of Cu migration leading to device performance degradation. In addition, it was found that Cu-doped CdTe samples exhibit a

  4. Smithsonian Astrophysical Observatory Ozone Mapping and Profiler Suite (SAO OMPS) formaldehyde retrieval

    NASA Astrophysics Data System (ADS)

    González Abad, Gonzalo; Vasilkov, Alexander; Seftor, Colin; Liu, Xiong; Chance, Kelly

    2016-07-01

    This paper presents our new formaldehyde (H2CO) retrievals, obtained from spectra recorded by the nadir instrument of the Ozone Mapping and Profiler Suite (OMPS) flown on board NASA's Suomi National Polar-orbiting Partnership (SUOMI-NPP) satellite. Our algorithm is similar to the one currently in place for the production of NASA's Ozone Monitoring Instrument (OMI) operational H2CO product. We are now able to produce a set of long-term data from two different instruments that share a similar concept and a similar retrieval approach. The ongoing overlap period between OMI and OMPS offers a perfect opportunity to study the consistency between both data sets. The different spatial and spectral resolution of the instruments is a source of discrepancy in the retrievals despite the similarity of the physic assumptions of the algorithm. We have concluded that the reduced spectral resolution of OMPS in comparison with OMI is not a significant obstacle in obtaining good-quality retrievals. Indeed, the improved signal-to-noise ratio of OMPS with respect to OMI helps to reduce the noise of the retrievals performed using OMPS spectra. However, the size of OMPS spatial pixels imposes a limitation in the capability to distinguish particular features of H2CO that are discernible with OMI. With root mean square (RMS) residuals ˜ 5 × 10-4 for individual pixels we estimate the detection limit to be about 7.5 × 1015 molecules cm-2. Total vertical column density (VCD) errors for individual pixels range between 40 % for pixels with high concentrations to 100 % or more for pixels with concentrations at or below the detection limit. We compare different OMI products (SAO OMI v3.0.2 and BIRA OMI v14) with our OMPS product using 1 year of data, between September 2012 and September 2013. The seasonality of the retrieved slant columns is captured similarly by all products but there are discrepancies in the values of the VCDs. The mean biases among the two OMI products and our OMPS product

  5. Smithsonian Astrophysical Observatory Ozone Mapping and Profiler Suite (SAO OMPS) formaldehyde retrieval

    NASA Astrophysics Data System (ADS)

    González Abad, G.; Vasilkov, A.; Seftor, C.; Liu, X.; Chance, K.

    2015-09-01

    This paper presents our new formaldehyde (H2CO) retrievals, obtained from spectra recorded by the nadir instrument of the Ozone Mapping and Profiler Suite (OMPS) flown on-board NASA's Suomi National Polar-orbiting Partnership (SUOMI-NPP) satellite. Our algorithm is similar to the one currently in place for the production of NASA's Ozone Monitoring Instrument (OMI) operational H2CO product. We are now able to produce a consistent set of long term data from two different instruments that share a similar concept. The ongoing overlap period between OMI and OMPS offers a perfect opportunity to study the consistency between both data sets. The different spatial and spectral resolution of the instruments is a source of discrepancy in the retrievals despite the similarity of the physic assumptions of the algorithm. We have concluded that the reduced spectral resolution of OMPS in comparison with OMI is not a significant obstacle in obtaining good quality retrievals. Indeed, the improved signal to noise ratio (SNR) of OMPS with respect to OMI helps to reduce the noise of the retrievals performed using OMPS spectra. However, the size of OMPS spatial pixels imposes a limitation in the capability to distinguish particular features of H2CO that are discernible with OMI. With root mean square (RMS) residuals ~ 5 × 10-4 for individual pixels we estimate the detection limit to be about 7.5 × 1015 molecules cm-2. Total vertical column densities (VCD) errors for individual pixels range between 40 % for pixels with high concentrations to 100 % or more for pixels with concentrations at or below the detection limit. We compare different OMI products with our OMPS product using one year of data, between September 2012 and September 2013. The seasonality of the retrieved slant columns is captured similarly by all products but there are discrepancies in the values of the VCDs. The mean biases among the two OMI products and our OMPS product are 21 % between OMI SAO and OMPS SAO and 38

  6. Tropospheric nitrogen dioxide column retrieval from ground-based zenith-sky DOAS observations

    NASA Astrophysics Data System (ADS)

    Tack, F.; Hendrick, F.; Goutail, F.; Fayt, C.; Merlaud, A.; Pinardi, G.; Hermans, C.; Pommereau, J.-P.; Van Roozendael, M.

    2015-06-01

    We present an algorithm for retrieving tropospheric nitrogen dioxide (NO2) vertical column densities (VCDs) from ground-based zenith-sky (ZS) measurements of scattered sunlight. The method is based on a four-step approach consisting of (1) the differential optical absorption spectroscopy (DOAS) analysis of ZS radiance spectra using a fixed reference spectrum corresponding to low NO2 absorption, (2) the determination of the residual amount in the reference spectrum using a Langley-plot-type method, (3) the removal of the stratospheric content from the daytime total measured slant column based on stratospheric VCDs measured at sunrise and sunset, and simulation of the rapid NO2 diurnal variation, (4) the retrieval of tropospheric VCDs by dividing the resulting tropospheric slant columns by appropriate air mass factors (AMFs). These steps are fully characterized and recommendations are given for each of them. The retrieval algorithm is applied on a ZS data set acquired with a multi-axis (MAX-) DOAS instrument during the Cabauw (51.97° N, 4.93° E, sea level) Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI) held from 10 June to 21 July 2009 in the Netherlands. A median value of 7.9 × 1015 molec cm-2 is found for the retrieved tropospheric NO2 VCDs, with maxima up to 6.0 × 1016 molec cm-2. The error budget assessment indicates that the overall error σTVCD on the column values is less than 28%. In the case of low tropospheric contribution, σTVCD is estimated to be around 39% and is dominated by uncertainties in the determination of the residual amount in the reference spectrum. For strong tropospheric pollution events, σTVCD drops to approximately 22% with the largest uncertainties on the determination of the stratospheric NO2 abundance and tropospheric AMFs. The tropospheric VCD amounts derived from ZS observations are compared to VCDs retrieved from off-axis and direct-sun measurements of the same MAX-DOAS instrument as well as to data

  7. Tropospheric nitrogen dioxide column retrieval from ground-based zenith-sky DOAS observations

    NASA Astrophysics Data System (ADS)

    Tack, F.; Hendrick, F.; Goutail, F.; Fayt, C.; Merlaud, A.; Pinardi, G.; Hermans, C.; Pommereau, J.-P.; Van Roozendael, M.

    2015-01-01

    We present an algorithm for retrieving tropospheric nitrogen dioxide (NO2) vertical column densities (VCDs) from ground-based zenith-sky (ZS) measurements of scattered sunlight. The method is based on a four-step approach consisting of (1) the Differential Optical Absorption Spectroscopy (DOAS) analysis of ZS radiance spectra using a fixed reference spectrum corresponding to low NO2 absorption, (2) the determination of the residual amount in the reference spectrum using a Langley-plot-type method, (3) the removal of the stratospheric content from the daytime total measured slant column based on stratospheric VCDs measured at sunrise and sunset, and simulation of the rapid NO2 diurnal variation, (4) the retrieval of tropospheric VCDs by dividing the resulting tropospheric slant columns by appropriate air mass factors (AMFs). These steps are fully characterized and recommendations are given for each of them. The retrieval algorithm is applied on a ZS dataset acquired with a Multi-AXis (MAX-) DOAS instrument during the Cabauw (51.97° N, 4.93° E, sea level) Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI) held from the 10 June to the 21 July 2009 in the Netherlands. A median value of 7.9 × 1015 molec cm-2 is found for the retrieved tropospheric NO2 VCDs, with maxima up to 6.0 × 1016 molec cm-2. The error budget assessment indicates that the overall error σTVCD on the column values is less than 28%. In case of low tropospheric contribution, σTVCD is estimated to be around 39% and is dominated by uncertainties in the determination of the residual amount in the reference spectrum. For strong tropospheric pollution events, σTVCD drops to approximately 22% with the largest uncertainties on the determination of the stratospheric NO2 abundance and tropospheric AMFs. The tropospheric VCD amounts derived from ZS observations are compared to VCDs retrieved from off-axis and direct-sun measurements of the same MAX-DOAS instrument as well as to

  8. Comparison of glyoxal, BrO, and IO vertical profiles derived from both ground-based and airborne MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Coburn, Sean; Volkamer, Rainer; Baidar, Sunil; Dix, Barbara; Koenig, Theodore; Ortega, Ivan; Sinreich, Roman; van Roozendael, Michel; Hendrick, Francois; Kinnison, Doug

    2015-04-01

    _ref based on the true atmospheric state; 2) through an iterative determination of SCD_ref based on the ground-based MAX-DOAS measurements and informed by an atmospheric model for consistency (in this case ground-based data is used from a deployment in Gulf Breeze, Florida, USA in conjunction with the Whole Atmosphere Community Climate Model - WACCM); and 3) through the fitting of the SCD_ref as an additional parameter in the determination of vertical column densities (VCD) as described in Theys et al., 2007.

  9. Water Treatment Unit Breadboard: Ground test facility for the recycling of urine and shower water for one astronaut

    NASA Astrophysics Data System (ADS)

    Lindeboom, Ralph E. F.; Lamaze, Brigitte; Clauwaert, Peter; Christiaens, Marlies E. R.; Rabaey, Korneel; Vlaeminck, Siegfried; Vanoppen, Marjolein; Demey, Dries; Farinas, Bernabé Alonso; Coessens, Wout; De Paepe, Jolien; Dotremont, Chris; Beckers, Herman; Verliefde, Arne

    2016-07-01

    One of the major challenges for long-term manned Space missions is the requirement of a regenerative life support system. Average water consumption in Western Countries is >100 L d-1. Even when minimizing the amount of water available per astronauts to 13 L d-1, a mission of 6 crew members requires almost 30 ton of fresh water supplies per year. Note that the International Space Station (ISS) weighs approximately 400 ton. Therefore the development of an efficient water recovery system is essential to future Space exploration. The ISS currently uses a Vapor Compression Distillation (VCD) unit following the addition of chromic and sulphuric acid for the microbial stabilization of urine (Carter, Tobias et al. 2012), yielding a water recovery percentage of only 70% due to scaling control. Additionally, Vapor Compression Distillation of 1.5 L urine cap 1 d-1 has a significantly higher power demand with 6.5 W cap-1 compared to a combination of electrodialysis (ED) and reverse osmosis (RO) with 1.9 and 0.6 W cap-1 respectively (Udert and Wächter 2012). A Water Treatment Unit Breadboard (WTUB) has been developed which combines a physicochemical and biological treatment. The aim was to recover 90% of the water in urine, condensate and shower water produced by one crew member and this life support testbed facility was inspired by the MELiSSA loop concept, ESA's Life Support System. Our experimental results showed that: 1) using a crystallisation reactor prior to the nitrification reduced scaling risks by Ca2+- and Mg2+ removal 2) the stabilization of urine diluted with condensate resulted in the biological conversion of 99% of Total Kjeldahl nitrogen into nitrate in the biological nitrification reactor 3) salinity and nitrate produced could be removed by 60-80% by electrodialysis, 4) shower water contaminated with skin microbiota and Neutrogena soap ® could be mixed with electrodialysis diluate and filtered directly over a ceramic nanofiltration at 93% water recovery and 5

  10. Circulation Type Classifications and their nexus to Van Bebber's storm track Vb

    NASA Astrophysics Data System (ADS)

    Hofstätter, M.; Chimani, B.

    2012-04-01

    Circulation Type Classifications (CTCs) are tools to identify repetitive and predominantly stationary patterns of the atmospheric circulation over a certain area, with the purpose to enable the recognition of specific characteristics in surface climate variables. On the other hand storm tracks can be used to identify similar types of synoptic events from a non-stationary, kinematic perspective. Such a storm track classification for Europe has been done in the late 19th century by Van Bebber (1882, 1891), from which the famous type Vb and Vc/d remained up to the present day because of to their association with major flooding events like in August 2002 in Europe. In this work a systematic tracking procedure has been developed, to determine storm track types and their characteristics especially for the Eastern Alpine Region in the period 1961-2002, using ERA40 and ERAinterim reanalysis. The focus thereby is on cyclone tracks of type V as suggested by van Bebber and congeneric types. This new catalogue is used as a reference to verify the hypothesis of a certain coherence of storm track Vb with certain circulation types (e.g. Fricke and Kaminski, 2002). Selected objective and subjective classification schemes from the COST733 action (http://cost733.met.no/, Phillip et al. 2010) are used therefore, as well as the manual classification from ZAMG (Lauscher 1972 and 1985), in which storm track Vb has been classified explicitly on a daily base since 1948. The latter scheme should prove itself as a valuable and unique data source in that issue. Results show that not less than 146 storm tracks are identified as Vb between 1961 and 2002, whereas only three events could be found from literature, pointing to big subjectivity and preconception in the issue of Vb storm tracks. The annual number of Vb storm tracks do not show any significant trend over the last 42 years, but large variations from year to year. Circulation type classification CAP27 (Cluster Analysis of Principal

  11. Explanation of red spectral shifts at CdTe grain boundaries

    NASA Astrophysics Data System (ADS)

    Moseley, John

    The best research-cell efficiencies for CdTe thin-film solar cells have recently increased from 17.3% to 20.4%. Despite these impressive recent gains, many improvements in device technology are necessary to reach the detailed-balance efficiency limit for CdTe-based (single-junction, non-concentrator) solar cells of ~32%. Improvements will increasingly rely on knowledge of the fundamental relationships between processing, electrical properties of defects, and device performance. In this study, scanning electron microscope (SEM)-based cathodoluminescence (CL) spectrum imaging was used to examine these fundamental relationships. In CL spectrum imaging we collect a spectrum per pixel in a 256 x 256 pixel SEM image by synchronizing a cryogenic silicon charge-coupled device with the electron-beam positioning. High spatial resolution photon energy maps obtained with this technique can reveal intricate luminescence phenomena that are not apparent in spectroscopic data. CL spectrum imaging was performed at T= 25 K on the back surface of CSS-deposited CdTe thin-films in a CdTe/CdS/SnO_2/glass configuration without back contacting. Both as-deposited and CdCl2 vapor-treated samples were analyzed. Luminescence emission is detected (bands) at ~1.32 eV and ~1.50 eV, which are consistent with Z- and Y-bands. The importance of the Z-band to CdTe solar cells is discussed. For the grains in the as-deposited films, there is a significant redshift in the transition energies near the grain boundaries. For the Z-band, this behavior is due to the effect of the high GB recombination velocity (sX~1x10 4 cm/s) in as-deposited CSS films on the donor-acceptor pair transition mechanism. The concentration of the shallow donor species participating in the Z-band transition was estimated to be ~1017 cm-3 . Based on this estimate, and the spatial correlation between the Z-band and the A-center (VCd-ClTe) complex transitions, ClTe is proposed as is the shallow donor species.

  12. Global Free Tropospheric NO2 Abundances Derived Using a Cloud Slicing Technique Applied to Satellite Observations from the Aura Ozone Monitoring Instrument (OMI)

    NASA Technical Reports Server (NTRS)

    Choi, S.; Joiner, J.; Choi, Y.; Duncan, B. N.; Bucsela, E.

    2014-01-01

    We derive free-tropospheric NO2 volume mixing ratios (VMRs) and stratospheric column amounts of NO2 by applying a cloud slicing technique to data from the Ozone Monitoring Instrument (OMI) on the Aura satellite. In the cloud-slicing approach, the slope of the above-cloud NO2 column versus the cloud scene pressure is proportional to the NO2 VMR. In this work, we use a sample of nearby OMI pixel data from a single orbit for the linear fit. The OMI data include cloud scene pressures from the rotational-Raman algorithm and above-cloud NO2 vertical column density (VCD) (defined as the NO2 column from the cloud scene pressure to the top-of-the-atmosphere) from a differential optical absorption spectroscopy (DOAS) algorithm. Estimates of stratospheric column NO2 are obtained by extrapolating the linear fits to the tropopause. We compare OMI-derived NO2 VMRs with in situ aircraft profiles measured during the NASA Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in 2006. The agreement is generally within the estimated uncertainties when appropriate data screening is applied. We then derive a global seasonal climatology of free-tropospheric NO2 VMR in cloudy conditions. Enhanced NO2 in the free troposphere commonly appears near polluted urban locations where NO2 produced in the boundary layer may be transported vertically out of the boundary layer and then horizontally away from the source. Signatures of lightning NO2 are also shown throughout low and middle latitude regions in summer months. A profile analysis of our cloud slicing data indicates signatures of uplifted and transported anthropogenic NO2 in the middle troposphere as well as lightning-generated NO2 in the upper troposphere. Comparison of the climatology with simulations from the Global Modeling Initiative (GMI) for cloudy conditions (cloud optical thicknesses > 10) shows similarities in the spatial patterns of continental pollution outflow. However, there are also some differences in

  13. Intrinsic propensities of amino acid residues in GxG peptides inferred from amide I' band profiles and NMR scalar coupling constants.

    PubMed

    Hagarman, Andrew; Measey, Thomas J; Mathieu, Daniel; Schwalbe, Harald; Schweitzer-Stenner, Reinhard

    2010-01-20

    A reliable intrinsic propensity scale of amino acid residues is indispensable for an assessment of how local conformational distributions in the unfolded state can affect the folding of peptides and proteins. Short host-guest peptides, such as GxG tripeptides, are suitable tools for probing such propensities. To explore the conformational distributions sampled by the central amino acid residue in these motifs, we combined vibrational (IR, Raman, and VCD) with NMR spectroscopy. The data were analyzed in terms of a superposition of two-dimensional Gaussian distribution functions in the Ramachandran space pertaining to subensembles of polyproline II, beta-strand, right- and left-handed helical, and gamma-turn-like conformations. The intrinsic propensities of eight amino acid residues (x = A, V, F, L, S, E, K, and M) in GxG peptides were determined as mole fractions of these subensembles. Our results show that alanine adopts primarily (approximately 80%) a PPII-like conformation, while valine and phenylalanine were found to sample PPII and beta-strand-like conformations equally. The centers of the respective beta-strand distributions generally do not coincide with canonical values of dihedral angles of residues in parallel or antiparallel beta-strands. In fact, the distributions for most residues found in the beta-region significantly overlap the PPII-region. A comparison with earlier reported results for trivaline reveals that the terminal valines increase the beta-strand propensity of the central valine residue even further. Of the remaining investigated amino acids, methionine preferred PPII the most (0.64), and E, S, L, and K exhibit moderate (0.56-0.45) PPII propensities. Residues V, F, S, E, and L sample, to a significant extent, a region between the canonical PPII and (antiparallel) beta-strand conformations. This region coincides with the sampling reported for L and V using theoretical predictions (Tran et al. Biochemistry 2005, 44, 11369). The distributions of

  14. Trend analysis of satellite-observed tropospheric NO2 vertical column densities over East Asia for 2005-2014

    NASA Astrophysics Data System (ADS)

    Muto, T.; Irie, H.; Itahashi, S.

    2015-12-01

    Nitrogen dioxide (NO2) plays a central role in the troposphere as a toxic substance for the respiratory system and a precursor for ozone and aerosols. Furthermore, the OH concentration is dependent on the NO2 concentration. While trend analysis for tropospheric NO2 concentrations in several specific regions all over the world was made in literature for period until 2011, the latest trends after 2011 have not been reported yet. The time period after 2011 is of interest, because it corresponds to the 12th 5-year-plan regulating NOx emissions in China and the period with the power substitution of thermal power generation for the nuclear power generation in Japan. In this study, we first compared satellite-observed tropospheric NO2 VCDs (Vertical Column Densities) with those observed by ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments installed at Chiba University in order to clarify whether or not there is degradation in OMI and GOME-2 NO2 VCDs data after 2011. We concluded that there is no significant degradation in OMI and GOME-2 data, since the comparison results are similar to those reported by previous validation studies. Based on the results, tropospheric NO2 VCD trends over Central Eastern China (CEC; 30-40°N, 110.0-123.0°E) and Japan (JPN; 33.5-37.0°N, 133.0-141.0°E) regions were estimated using the regression analysis for annual mean values. Although an increase in NO2 VCDs occurred at a rate of 6%(8%) per year in OMI (GOME-2) data from 2005(2007) to 2011 over CEC, we found a decrease at a rate of 10%(11%) per year from 2011 to 2014. This reduction may be a result from the regulation of NOx emissions from coal fired power generation, iron foundry, cement plant, etc., and installation of the denitrification units during the period of 12th 5-year-plan. For JPN, both OMI and GOME-2 data sets showed that the NO2 VCDs decreased at a rate of 4% per year before 2011. The decreasing trends continued until 2014, with a

  15. Validation opportunities of DOAS Network in Moscow Region

    NASA Astrophysics Data System (ADS)

    Borovski, Alexander; Postylyakov, Oleg; Elokhov, Alexander; Ivanov, Victor; Kanaya, Yugo

    A.M. Obukhov Institute of Atmospheric Physics (IAP) of Russian Academy of Science developed a network of atmosphere composition measurements by DOAS method. Measurements sites of the network are located in the centre of Moscow at IAP (55.74N, 37.62E) south-east part of the city at M.V. Lomonosov Moscow State University (55.70N 37.53E), and in background region at Zvenigorod Scientific Station of IAP (ZSS, 55.70N, 36.78E). Intensity of the scattered solar radiation is registered in ultra-violet and visible spectrum region. Three devices are mounted at ZSS: based on MDR-23 spectrometer (since 1990), JAMSTEC MAX-DOAS (since 2008), and based on ORIEL MS257 spectrometer (since 2008). ORIEL MS260i imaging spectrometers were mounted at city stations in 2010. Measurements are regular and continuous at all stations. Basing on performed measurements of spectral radiance, the vertical distribution at twilight, the total content and the integral content in the boundary layer (ABL) in daytime of NO2 are obtained. The quantities are obtained in clear sky and cloudy conditions. Besides that, the vertical distribution of aerosol and the total content (mainly contributed by ABL) of HCHO using MAX-DOAS are calculated. The HCHO total content is retrieved with error about 20 %. We analyzed the variability of the HCHO during clear sky conditions in 2010. The HCHO content is larger during east wind directions than during non-east wind directions. It can be associated with Moscow Megacity influence on air quality at Zvenigorod. The estimation of Moscow Megacity influence on HCHO abundance at Zvenigorod is around 2.5E14 mol/cm2 per 1 km length of trajectory path inside Moscow Ring Road. Our data show statistically significant positive temperature effect in HCHO for the background condition for temperatures from -5C to +33C. The temperature trend in HCHO data at ZSS is about (8.9±2.3)E14 mol/cm2/C. The increase of the HCHO VCD during increase of the air temperature can be explained by the

  16. MAX-DOAS observations and their application to the validation of satellite and model data in Wuxi, China

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Wagner, T.; Xie, P.; Theys, N.; De Smedt, I.; Koukouli, M.; Stavrakou, T.; Beirle, S.; Li, A.

    2015-12-01

    effect of the aerosols on the satellite cloud retrievals and the corresponding errors of the tropospheric AMF of the trace gases. Here should be noted that aerosol effects on the AMF is not yet considered in the published satellite products, which can cause appreciable errors of the tropospheric VCD of satellite products around polluted regions.

  17. Aircraft measurements of BrO, IO, glyoxal, NO2, H2O, O2-O2 and aerosol extinction profiles in the tropics: comparison with aircraft-/ship-based in situ and lidar measurements

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-05-01

    -enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and aircraft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500 m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 1013 molec cm-2 (RF12) and at least 0.5 x 1013 molec cm-2 (RF17, 0-10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 1012 molec cm-2 (RF12) and 2.5 x 1012 molec cm-2 (RF17) and glyoxal VCDs of 2.6 x 1014 molec cm-2 (RF12) and 2.7 x 1014 molec cm-2 (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1-0.2 pptv; glyoxal: 52 ± 5%, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.

  18. Aircraft Measurements of BrO, IO, Glyoxal, NO2, H2O, O2-O2 and Aerosol Extinction Profiles in the Tropics: Comparison with Aircraft-/Ship-Based in Situ and Lidar Measurements

    NASA Technical Reports Server (NTRS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-01-01

    -enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and air-craft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6 deg N; 101.2 to 97.4 deg W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 10(exp 13) molec cm(exp -2) (RF12) and at least 0.5 x 10(exp 13) molec cm(exp -2) (RF17, 0- 10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 10(exp 12) molec cm(exp -2) (RF12) and 2.5 x 10(exp 12) molec cm(exp -2) (RF17) and glyoxal VCDs of 2.6 x 10(exp 14) molec cm(exp -2) (RF12) and 2.7 x 10(exp 14) molec cm(exp -2) (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 plus or minus 5 %, 0.1-0.2 pptv; glyoxal: 52 plus or minus 5 %, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.

  19. Triaspartate: a model system for conformationally flexible DDD motifs in proteins.

    PubMed

    Duitch, Laura; Toal, Siobhan; Measey, Thomas J; Schweitzer-Stenner, Reinhard

    2012-05-01

    Understanding the interactions that govern turn formation in the unfolded state of proteins is necessary for a complete picture of the role that these turns play in both normal protein folding and functionally relevant yet disordered linear motifs. It is still unclear, however, whether short peptides can adopt stable turn structures in aqueous environments in the absence of any nonlocal interactions. To explore the effect that nearest-neighbor interactions and the local peptide environment have on the turn-forming capability of individual amino acid residues in short peptides, we combined vibrational (IR, Raman, and VCD), UV-CD, and (1)H NMR spectroscopies in order to probe the conformational ensemble of the central aspartic acid residue of the triaspartate peptide (DDD). The study was motivated by the recently discovered turn propensities of aspartic acid in GDG (Hagarman; et al. Chem.-Eur. J. 2011, 17, 6789). We investigated the DDD peptide under both acidic and neutral conditions in order to elucidate the effect that side-chain protonation has on the conformational propensity of the central aspartic acid residue. Amide I' profiles were analyzed in terms of two-dimensional Gaussian distributions representing conformational subdistributions in Ramachandran space. Interestingly, our results show that while the protonated form of the DDD peptide samples various turn-like conformations similar to GDG, deprotonation of the peptide eliminates this propensity for turns, causing the fully ionized peptide to exclusively sample pPII and β-strand-like structures. To further explore the factors stabilizing these more extended conformations in fully ionized DDD, we analyzed the temperature dependence of both the UV-CD spectrum and the (3)J(H(N),H(α)) coupling constants of the two amide protons (N- and C-terminal) in terms of a simple two-state (pPII-β) thermodynamic model. Thus, we were able to obtain the enthalpic and entropic differences between the pPII and

  20. Mercury oxidation from bromine chemistry in the free troposphere over the southeastern US

    NASA Astrophysics Data System (ADS)

    Coburn, S.; Dix, B.; Edgerton, E.; Holmes, C. D.; Kinnison, D.; Liang, Q.; ter Schure, A.; Wang, S.; Volkamer, R.

    2015-10-01

    The elevated deposition of atmospheric mercury over the Southeastern United States is currently not well understood. Here we measure partial columns and vertical profiles of bromine monoxide (BrO) radicals, a key component of mercury oxidation chemistry, to better understand the processes and altitudes at which mercury is being oxidized in the atmosphere. We use the data from a ground-based MAX-DOAS instrument located at a coastal site ~ 1 km from the Gulf of Mexico in Gulf Breeze, FL, where we had previously detected tropospheric BrO (Coburn et al., 2011). Our profile retrieval assimilates information about stratospheric BrO from the WACCM chemical transport model, and uses only measurements at moderately low solar zenith angles (SZA) to estimate the BrO slant column density contained in the reference spectrum (SCDRef). The approach has 2.6 degrees of freedom, and avoids spectroscopic complications that arise at high SZA; knowledge about SCDRef helps to maximize sensitivity in the free troposphere (FT). A cloud-free case study day with low aerosol load (9 April 2010) provided optimal conditions for distinguishing marine boundary layer (MBL: 0-1 km) and free tropospheric (FT: 1-15 km) BrO from the ground. The average daytime tropospheric BrO vertical column density (VCD) of ~ 2.3 × 1013 molec cm-2 (SZA < 70°) is consistent with our earlier reports on other days. The vertical profile locates essentially all tropospheric BrO above 4 km, and shows no evidence for BrO inside the MBL (detection limit < 0.5 pptv). BrO increases in the FT. The average FT-BrO mixing ratio was ~ 0.9 pptv between 1-15 km, consistent with recent aircraft observations. We find that the oxidation of gaseous elemental mercury (GEM) by bromine radicals to form gaseous oxidized mercury (GOM) is the dominant pathway for GEM oxidation throughout the troposphere above Gulf Breeze. The column integral oxidation rates range from 3.0-3.4 × 105 molec cm-2 s-1 for bromine, while contributions from

  1. Mercury oxidation from bromine chemistry in the free troposphere over the southeastern US

    NASA Astrophysics Data System (ADS)

    Coburn, Sean; Dix, Barbara; Edgerton, Eric; Holmes, Christopher D.; Kinnison, Douglas; Liang, Qing; ter Schure, Arnout; Wang, Siyuan; Volkamer, Rainer

    2016-03-01

    The elevated deposition of atmospheric mercury over the southeastern United States is currently not well understood. Here we measure partial columns and vertical profiles of bromine monoxide (BrO) radicals, a key component of mercury oxidation chemistry, to better understand the processes and altitudes at which mercury is being oxidized in the atmosphere. We use data from a ground-based MAX-DOAS instrument located at a coastal site ˜ 1 km from the Gulf of Mexico in Gulf Breeze, FL, where we had previously detected tropospheric BrO (Coburn et al., 2011). Our profile retrieval assimilates information about stratospheric BrO from the WACCM chemical transport model (CTM), and uses only measurements at moderately low solar zenith angles (SZAs) to estimate the BrO slant column density contained in the reference spectrum (SCDRef). The approach has 2.6 degrees of freedom, and avoids spectroscopic complications that arise at high SZA; knowledge about SCDRef further helps to maximize sensitivity in the free troposphere (FT). A cloud-free case study day with low aerosol load (9 April 2010) provided optimal conditions for distinguishing marine boundary layer (MBL: 0-1 km) and free-tropospheric (FT: 1-15 km) BrO from the ground. The average daytime tropospheric BrO vertical column density (VCD) of ˜ 2.3 × 1013 molec cm-2 (SZA < 70°) is consistent with our earlier reports on other days. The vertical profile locates essentially all tropospheric BrO above 4 km, and shows no evidence for BrO inside the MBL (detection limit < 0.5 pptv). BrO increases to ˜ 3.5 pptv at 10-15 km altitude, consistent with recent aircraft observations. Our case study day is consistent with recent aircraft studies, in that the oxidation of gaseous elemental mercury (GEM) by bromine radicals to form gaseous oxidized mercury (GOM) is the dominant pathway for GEM oxidation throughout the troposphere above Gulf Breeze. The column integral oxidation rates are about 3.6 × 105 molec cm-2 s-1 for bromine

  2. U.S. NO2 trends (2005-2013): EPA Air Quality System (AQS) data versus improved observations from the Ozone Monitoring Instrument (OMI)

    NASA Astrophysics Data System (ADS)

    Lamsal, Lok N.; Duncan, Bryan N.; Yoshida, Yasuko; Krotkov, Nickolay A.; Pickering, Kenneth E.; Streets, David G.; Lu, Zifeng

    2015-06-01

    Emissions of nitrogen oxides (NOx) and, subsequently, atmospheric levels of nitrogen dioxide (NO2) have decreased over the U.S. due to a combination of environmental policies and technological change. Consequently, NO2 levels have decreased by 30-40% in the last decade. We quantify NO2 trends (2005-2013) over the U.S. using surface measurements from the U.S. Environmental Protection Agency (EPA) Air Quality System (AQS) and an improved tropospheric NO2 vertical column density (VCD) data product from the Ozone Monitoring Instrument (OMI) on the Aura satellite. We demonstrate that the current OMI NO2 algorithm is of sufficient maturity to allow a favorable correspondence of trends and variations in OMI and AQS data. Our trend model accounts for the non-linear dependence of NO2 concentration on emissions associated with the seasonal variation of the chemical lifetime, including the change in the amplitude of the seasonal cycle associated with the significant change in NOx emissions that occurred over the last decade. The direct relationship between observations and emissions becomes more robust when one accounts for these non-linear dependencies. We improve the OMI NO2 standard retrieval algorithm and, subsequently, the data product by using monthly vertical concentration profiles, a required algorithm input, from a high-resolution chemistry and transport model (CTM) simulation with varying emissions (2005-2013). The impact of neglecting the time-dependence of the profiles leads to errors in trend estimation, particularly in regions where emissions have changed substantially. For example, trends calculated from retrievals based on time-dependent profiles offer 18% more instances of significant trends and up to 15% larger total NO2 reduction versus the results based on profiles for 2005. Using a CTM, we explore the theoretical relation of the trends estimated from NO2 VCDs to those estimated from ground-level concentrations. The model-simulated trends in VCDs strongly

  3. Examining the role of sea ice and meteorology in Arctic boundary layer halogen chemistry

    NASA Astrophysics Data System (ADS)

    Peterson, Peter Kevin

    distributions of BrO are influenced by atmospheric stability. We found minimal influence of wind speed on either lower-tropospheric bromine activation (LT-VCD) or the vertical distribution of BrO, while examination of seasonal trends and the temperature dependence of the vertical distribution support the finding that atmospheric stability affects the distribution of BrO. While shallow layer events have higher concentrations of halogens, distributed column events tend to have higher overall amounts of activation, implying that in situ near surface measurements may be insufficient to constrain the role of environmental parameters in the activation of halogens. Examination of multiple years of data at Barrow, Alaska shows that time spent in first year ice (FYI) areas is weakly linearly correlated (R=0.38) with the activation of BrO. However, examining annual averages of BrO shows that despite the non-linear relationship between time in FYI areas and BrO, time spent in FYI areas still influences the interannual variability of BrO.

  4. U.S. NO₂ trends (2005–2013): EPA air quality system (AQS) data versus improved observations from the Ozone Monitoring Instrument (OMI)

    SciTech Connect

    Lamsal, Lok N.; Duncan, Bryan N.; Yoshida, Yasuko; Krotkov, Nickolay A.; Pickering, Kenneth E.; Streets, David G.; Lu, Zifeng

    2015-06-01

    Emissions of nitrogen oxides (NOx) and, subsequently, atmospheric levels of nitrogen dioxide (NO₂) have decreased over the U.S. due to a combination of environmental policies and technological change. Consequently, NO₂ levels have decreased by 30–40% in the last decade. We quantify NO₂ trends (2005–2013) over the U.S. using surface measurements from the U.S. Environmental Protection Agency (EPA) Air Quality System (AQS) and an improved tropospheric NO₂ vertical column density (VCD) data product from the Ozone Monitoring Instrument (OMI) on the Aura satellite.We demonstrate that the current OMI NO₂ algorithm is of sufficient maturity to allow a favorable correspondence of trends and variations in OMI and AQS data. Our trend model accounts for the non-linear dependence of NO₂ concentration on emissions associated with the seasonal variation of the chemical lifetime, including the change in the amplitude of the seasonal cycle associated with the significant change in NOx emissions that occurred over the last decade. The direct relationship between observations and emissions becomes more robust when one accounts for these non-linear dependencies. We improve the OMI NO₂ standard retrieval algorithm and, subsequently, the data product by using monthly vertical concentration profiles, a required algorithm input, from a high-resolution chemistry and transport model (CTM) simulation with varying emissions (2005-2013). The impact of neglecting the time-dependence of the profiles leads to errors in trend estimation, particularly in regions where emissions have changed substantially. For example, trends calculated from retrievals based on time-dependent profiles offer 18% more instances of significant trends and up to 15% larger total NO₂ reduction versus the results based on profiles for 2005. Using a CTM, we explore the theoretical relation of the trends estimated from NO₂ VCDs to those estimated from ground-level concentrations

  5. U.S. NO₂ trends (2005–2013): EPA air quality system (AQS) data versus improved observations from the Ozone Monitoring Instrument (OMI)

    DOE PAGES

    Lamsal, Lok N.; Duncan, Bryan N.; Yoshida, Yasuko; Krotkov, Nickolay A.; Pickering, Kenneth E.; Streets, David G.; Lu, Zifeng

    2015-06-01

    Emissions of nitrogen oxides (NOx) and, subsequently, atmospheric levels of nitrogen dioxide (NO₂) have decreased over the U.S. due to a combination of environmental policies and technological change. Consequently, NO₂ levels have decreased by 30–40% in the last decade. We quantify NO₂ trends (2005–2013) over the U.S. using surface measurements from the U.S. Environmental Protection Agency (EPA) Air Quality System (AQS) and an improved tropospheric NO₂ vertical column density (VCD) data product from the Ozone Monitoring Instrument (OMI) on the Aura satellite.We demonstrate that the current OMI NO₂ algorithm is of sufficient maturity to allow a favorable correspondence of trendsmore » and variations in OMI and AQS data. Our trend model accounts for the non-linear dependence of NO₂ concentration on emissions associated with the seasonal variation of the chemical lifetime, including the change in the amplitude of the seasonal cycle associated with the significant change in NOx emissions that occurred over the last decade. The direct relationship between observations and emissions becomes more robust when one accounts for these non-linear dependencies. We improve the OMI NO₂ standard retrieval algorithm and, subsequently, the data product by using monthly vertical concentration profiles, a required algorithm input, from a high-resolution chemistry and transport model (CTM) simulation with varying emissions (2005-2013). The impact of neglecting the time-dependence of the profiles leads to errors in trend estimation, particularly in regions where emissions have changed substantially. For example, trends calculated from retrievals based on time-dependent profiles offer 18% more instances of significant trends and up to 15% larger total NO₂ reduction versus the results based on profiles for 2005. Using a CTM, we explore the theoretical relation of the trends estimated from NO₂ VCDs to those estimated from ground-level concentrations. The model

  6. Creating and Implementing a Regularized Monitoring and EnforcementSystem for China's Mandatory Standards and Energy Information Label forAppliances

    SciTech Connect

    Lin, Jiang

    2007-03-01

    China has developed a comprehensive program of energy efficiency standards and labels for household appliances. In 1989, China first launched its minimum energy performance standards (MEPS), which are now applied to an extensive list of products. In 1998, China launched a voluntary energy endorsement label, which has grown to cover both energy-saving and water-saving products. And, in 2005, China launched a mandatory energy information label that initially covered two products. CLASP has assisted China in developing 11 minimum energy performance standards (MEPS) for 9 products and endorsement labels for 11 products including: refrigerators; air conditioners; televisions; printers; computers; monitors; fax machines; copiers; DVD/VCD players; external power supplies; and set-top boxes. CLASP has also assisted China in the development of the mandatory energy information label. Increasingly, attention is being placed on maximum energy savings from China's standards and labeling (S&L) efforts in order to meet the recently announced goal of reducing China's energy intensity by 20 percent by 2010 with an interim objective of 4 percent in 2006. China's mandatory standards system is heavily focused on the technical requirements for efficiency performance, but historically, it has lacked administrative and personnel capacity to undertake monitoring and enforcement of these legally binding standards. Similarly, resources for monitoring and enforcement have been quite limited. As a consequence, compliance to both the mandatory standards and the mandatory energy information label is uneven with the potential and likely result of lost energy savings. Thus, a major area for improvement, which could significantly increase overall energy savings, is the creation and implementation of a regularized monitoring system for tracking the compliance to, and enforcement of, mandatory standards and the energy information label in China. CLASP has been working with the China National