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Sample records for 4-vinylcyclohexene diepoxide vcd

  1. 4-Vinylcyclohexene diepoxide (VCD) inhibits mammary epithelial differentiation and induces fibroadenoma formation in female Sprague Dawley rats.

    PubMed

    Wright, Laura E; Frye, Jennifer B; Lukefahr, Ashley L; Marion, Samuel L; Hoyer, Patricia B; Besselsen, David G; Funk, Janet L

    2011-07-01

    4-Vinylcyclohexene diepoxide (VCD), an occupational chemical that targets ovarian follicles and accelerates ovarian failure in rodents, was used to test the effect of early-onset reproductive senescence on mammary fibroadenoma formation. One-month female Sprague Dawley rats were dosed with VCD (80 mg/kg or 160 mg/kg) and monitored for 22 months for persistent estrus and tumor development. Only high-dose VCD treatment accelerated the onset of persistent estrus relative to controls. However, both doses of VCD accelerated mammary tumor onset by 5 months, increasing incidence to 84% (vs. 38% in controls). Tumor development was independent of time in persistent estrus, 17 β-estradiol, androstenedione and prolactin. Delay in VCD administration until after completion of mammary epithelial differentiation (3 months) did not alter tumor formation despite acceleration of ovarian senescence. VCD administration to 1-month rats acutely decreased mammary alveolar bud number and expression of β-casein, suggesting that VCD's tumorigenic effect requires exposure during mammary epithelial differentiation.

  2. 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.

  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. 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.

  5. Parabens Accelerate Ovarian Dysfunction in a 4-Vinylcyclohexene Diepoxide-Induced Ovarian Failure Model

    PubMed Central

    Lee, Jae-Hwan; Lee, Myeongho; Ahn, Changhwan; Kang, Hee Young; Tran, Dinh Nam; Jeung, Eui-Bae

    2017-01-01

    Parabens are widely used preservatives in basic necessities such as cosmetic and pharmaceutical products. In previous studies, xenoestrogenic actions of parabens were reported in an immature rat model and a rat pituitary cell line (GH3 cells). The relationship between parabens and ovarian failure has not been described. In the present study, the influence of parabens on ovarian folliculogenesis and steroidogenesis was investigated. A disruptor of ovarian small pre-antral follicles, 4-vinylcyclohexene diepoxide (VCD, 40 mg/kg), was used to induce premature ovarian failure (POF). Methylparaben (MP, 100 mg/kg), propylparaben (PP, 100 mg/kg), and butylparaben (BP, 100 mg/kg) dissolved in corn oil were treated in female 8-week-old Sprague-Dawley rat for 5 weeks. Estrus cycle status was checked daily by vaginal smear test. Ovarian follicle development and steroid synthesis were investigated through real-time PCR and histological analyses. Diestrus phases in the VCD, PP, and BP groups were longer than that in the vehicle group. VCD significantly decreased mRNA level of folliculogenesis-related genes (Foxl2, Kitl and Amh). All parabens significantly increased the Amh mRNA level but unchanged Foxl2 and Kitlg acting in primordial follicles. VCD and MP slightly increased Star and Cyp11a1 levels, which are related to an initial step in steroidogenesis. VCD and parabens induced an increase in FSH levels in serum and significantly decreased the total number of follicles. Increased FSH implies impairment in ovarian function due to VCD or parabens. These results suggest that VCD may suppress both formation and development of follicles. In particular, combined administration of VCD and parabens accelerated inhibition of the follicle-developmental process through elevated AMH level in small antral follicles. PMID:28208728

  6. Parabens Accelerate Ovarian Dysfunction in a 4-Vinylcyclohexene Diepoxide-Induced Ovarian Failure Model.

    PubMed

    Lee, Jae-Hwan; Lee, Myeongho; Ahn, Changhwan; Kang, Hee Young; Tran, Dinh Nam; Jeung, Eui-Bae

    2017-02-08

    Parabens are widely used preservatives in basic necessities such as cosmetic and pharmaceutical products. In previous studies, xenoestrogenic actions of parabens were reported in an immature rat model and a rat pituitary cell line (GH3 cells). The relationship between parabens and ovarian failure has not been described. In the present study, the influence of parabens on ovarian folliculogenesis and steroidogenesis was investigated. A disruptor of ovarian small pre-antral follicles, 4-vinylcyclohexene diepoxide (VCD, 40 mg/kg), was used to induce premature ovarian failure (POF). Methylparaben (MP, 100 mg/kg), propylparaben (PP, 100 mg/kg), and butylparaben (BP, 100 mg/kg) dissolved in corn oil were treated in female 8-week-old Sprague-Dawley rat for 5 weeks. Estrus cycle status was checked daily by vaginal smear test. Ovarian follicle development and steroid synthesis were investigated through real-time PCR and histological analyses. Diestrus phases in the VCD, PP, and BP groups were longer than that in the vehicle group. VCD significantly decreased mRNA level of folliculogenesis-related genes (Foxl2, Kitl and Amh). All parabens significantly increased the Amh mRNA level but unchanged Foxl2 and Kitlg acting in primordial follicles. VCD and MP slightly increased Star and Cyp11a1 levels, which are related to an initial step in steroidogenesis. VCD and parabens induced an increase in FSH levels in serum and significantly decreased the total number of follicles. Increased FSH implies impairment in ovarian function due to VCD or parabens. These results suggest that VCD may suppress both formation and development of follicles. In particular, combined administration of VCD and parabens accelerated inhibition of the follicle-developmental process through elevated AMH level in small antral follicles.

  7. 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.

  8. 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.

  9. Differences between rats and mice in the involvement of the aryl hydrocarbon receptor in 4-vinylcyclohexene diepoxide-induced ovarian follicle loss

    SciTech Connect

    Thompson, Kary E.; Bourguet, Shannon M.; Christian, Patricia J.; Benedict, Jamie C.; Sipes, I. Glenn; Flaws, Jodi A.; Hoyer, Patricia B. . E-mail: hoyer@u.arizona.edu

    2005-03-01

    Repeated dosing with the occupational chemical 4-vinylcyclohexene diepoxide (VCD) selectively depletes small pre-antral follicles in the ovaries of rats and mice via apoptosis. The aryl hydrocarbon receptor (AhR) plays a role in mediating the effects of several xenobiotics. Therefore, this study was designed to investigate a potential role of the AhR in VCD-induced ovotoxicity. Female F344 rats, C57BL/6 mice, or AhR-deficient (-/-, AhRKO) mice were dosed daily (15 days) with vehicle, VCD (80 mg/kg, i.p.) and/or the AhR antagonist, alpha-naphthoflavone (ANF; 80 mg/kg, i.p.). Compared with controls, VCD caused a 60% reduction (P < 0.05) in primordial and primary follicles in mice and rats. Concurrent dosing with ANF protected against the VCD-induced follicle loss in rats, but not in mice. As with AhR-intact mice and rats, VCD induced a 70% loss (P < 0.05) of small pre-antral follicles in AhRKO mice. AhR mRNA expression was increased (P < 0.05) by VCD dosing in small pre-antral follicles isolated from ovaries of rats but not mice. AhR protein in rats was increased by VCD dosing in oocyte nuclei in primordial and primary follicles when measured by immunofluorescence and confocal microscopy. In rat small pre-antral follicles, apoptosis-associated caspase-3-like activity was increased (P < 0.05) by VCD treatment, decreased (P < 0.05) by ANF treatment, and unaffected by VCD plus ANF treatment. VCD had no effect on expression of GST Ya1 or GST Ya2 mRNA or CYP 1A1 protein in rats. Taken together, these findings demonstrate a difference between rats and mice in the potential involvement of AhR as related to VCD-induced ovotoxicity. Whereas, AhR appears to be involved in rats, no evidence for a similar role in mice was obtained. Overall, these findings point out that there can be mechanistic species differences in ovarian responses to xenobiotic chemicals.

  10. 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.

  11. Conditions and possible mechanisms of VCD-induced ovarian failure.

    PubMed

    Liu, Wei; Wang, Ling-Yan; Xing, Xiao-Xue; Fan, Guan-Wei

    2015-12-01

    Perimenopause is an important period in women's lives, in which they experience a series of physiological changes. Current animal models of perimenopause fail to adequately replicate this particular stage in female life, while current in vitro models are too simplistic and cannot account for systemic effects. Neither the naturally-ageing animal model, nor the ovariectomised animal model, mimic the natural transitional process that is the menopause. In vivo and in vitro studies have confirmed that the occupational chemical, 4-vinylcyclohexene diepoxide (VCD), can cause selective destruction of the ovarian primordial and primary follicles of rats and mice by accelerating the apoptotic process, which successfully mimics the perimenopausal state in women. However, it is the in vivo VCD-induced rodent perimenopausal models that are currently the most widely used in research, rather than any of the available in vitro models. Studies on the mechanisms involved have found that VCD induces ovotoxicity via interference with the c-kit/kit ligand and apoptotic signalling pathways, among others. Overall, the VCD-induced perimenopausal animal models have provided some insight into female perimenopause, but they are far from ideal models of the human situation.

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

    PubMed

    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.

  13. Effect of CYP2E1 gene deletion in mice on expression of microsomal epoxide hydrolase in response to VCD exposure.

    PubMed

    Keating, Aileen F; Rajapaksa, Kathila S; Sipes, I Glenn; Hoyer, Patricia B

    2008-10-01

    Females are born with a finite number of primordial follicles. 4-Vinylcyclohexene diepoxide (VCD) is a metabolite formed by epoxidation of 4-vinylcyclohexene (VCH) via its two monoepoxides 1,2- and 7,8-4-vinylcyclohexene monoepoxide (VCM). VCD specifically destroys small preantral (primordial and small primary) follicles in the rodent ovary. The phase I enzyme, cytochrome P450 isoform 2E1 (CYP2E1) is involved in ovarian metabolism of VCM to VCD. Further, microsomal epoxide hydrolase (mEH) can detoxify VCD to an inactive tetrol (4-(1,2-dihydroxy)ethyl-1,2-dihydroxycyclohexane). This study evaluated the effects of VCD-induced ovotoxicity on mEH in CYP2E1+/+ and -/- mice (129S(1)/SvImJ background strain) using a postnatal day 4 mouse whole ovary culture system. The hypothesis of our study is that there is a relationship between CYP2E1 and mEH gene expression in the mouse ovary. Relative to control, VCD exposure caused follicle loss (p < 0.05) in ovaries from both genotypes; however, after 15 days, this loss was greater (p < 0.05) in CYP2E1+/+ ovaries. In a time course (2-15 days), relative to control, VCD (5 microM) caused an increase (p < 0.05) in mEH mRNA by 0.5-fold (day 10) and 1.84-fold (day 15) in CYP2E1-/- but not +/+ ovaries. 7,12-Dimethylbenz[a]anthracene (DMBA) also destroys ovarian follicles but, unlike VCD, is bioactivated by mEH to an ovotoxic 3,4-diol-1,2-epoxide metabolite. Incubation of ovaries in increasing concentrations of DMBA (0.5-1 microM, 15 days) resulted in greater (p < 0.05) follicle loss in CYP2E1-/-, relative to +/+ ovaries. With greater mEH (CYP2E1-/-), increased follicle loss with DMBA (bioactivation) and decreased follicle loss with VCD (detoxification) support that ovarian expression of CYP2E1 and mEH may be linked.

  14. Dual protective role for glutathione S-transferase class pi against VCD-induced ovotoxicity in the rat ovary.

    PubMed

    Keating, Aileen F; Sen, Nivedita; Sipes, I Glenn; Hoyer, Patricia B

    2010-09-01

    The occupational chemical 4-vinylcyclohexene diepoxide (VCD) selectively destroys ovarian small pre-antral follicles in rats and mice via apoptosis. Detoxification of VCD can occur through glutathione conjugation, catalyzed by glutathione S-transferase (GST) enzymes. Further, GST class pi (GSTp) can negatively regulate JNK activity through protein:protein interactions in extra-ovarian tissues. Dissociation of this protein complex in the face of chemical exposure releases the inhibition of pro-apoptotic JNK. Increased JNK activity during VCD-induced ovotoxicity has been shown in isolated ovarian small pre-antral follicles following in vivo dosing of rats (80mg/kg/day; 15days, i.p.). The present study investigated the pattern of ovarian GSTp expression during VCD exposure. Additionally, the effect of VCD on an ovarian GSTp:JNK protein complex was investigated. PND4 F344 rat ovaries were incubated in control medium+/-VCD (30muM) for 2-8days. VCD increased ovarian GSTp mRNA (P <0.05) relative to control on d4-d8; whereas GSTp protein was increased (P<0.05) on d6-d8. A GSTp:JNK protein complex was detected by immunoprecipitation and Western blotting in ovarian tissues. Relative to control, the amount of GSTp-bound JNK was increased (P=0.09), while unbound JNK was decreased (P<0.05) on d6 of VCD exposure. The VCD-induced decrease in unbound JNK was preceded by a decrease in phosphorylated c-Jun which occurred on d4. These findings are in support of a possible dual protective role for GSTp in the rat ovary, consisting of metabolism of VCD and inhibition of JNK-initiated apoptosis.

  15. Dual protective role for Glutathione S-transferase class pi against VCD-induced ovotoxicity in the rat ovary

    SciTech Connect

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

    2010-09-01

    The occupational chemical 4-vinylcyclohexene diepoxide (VCD) selectively destroys ovarian small pre-antral follicles in rats and mice via apoptosis. Detoxification of VCD can occur through glutathione conjugation, catalyzed by glutathione S-transferase (GST) enzymes. Further, GST class pi (GSTp) can negatively regulate JNK activity through protein:protein interactions in extra-ovarian tissues. Dissociation of this protein complex in the face of chemical exposure releases the inhibition of pro-apoptotic JNK. Increased JNK activity during VCD-induced ovotoxicity has been shown in isolated ovarian small pre-antral follicles following in vivo dosing of rats (80 mg/kg/day; 15 days, i.p.). The present study investigated the pattern of ovarian GSTp expression during VCD exposure. Additionally, the effect of VCD on an ovarian GSTp:JNK protein complex was investigated. PND4 F344 rat ovaries were incubated in control medium {+-} VCD (30 {mu}M) for 2-8 days. VCD increased ovarian GSTp mRNA (P < 0.05) relative to control on d4-d8; whereas GSTp protein was increased (P < 0.05) on d6-d8. A GSTp:JNK protein complex was detected by immunoprecipitation and Western blotting in ovarian tissues. Relative to control, the amount of GSTp-bound JNK was increased (P = 0.09), while unbound JNK was decreased (P < 0.05) on d6 of VCD exposure. The VCD-induced decrease in unbound JNK was preceded by a decrease in phosphorylated c-Jun which occurred on d4. These findings are in support of a possible dual protective role for GSTp in the rat ovary, consisting of metabolism of VCD and inhibition of JNK-initiated apoptosis.

  16. 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.

  17. Expression of ovarian microsomal epoxide hydrolase and glutathione S-transferase during onset of VCD-induced ovotoxicity in B6C3F(1) mice.

    PubMed

    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(1) mice were incubated with VCD (15 microM) 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.

  18. 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.

  19. Distribution and responsiveness of rat anti-Müllerian hormone during ovarian development and VCD-induced ovotoxicity.

    PubMed

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

    2010-11-15

    Anti-Müllerian 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 μM, 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 μM) 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.

  20. 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.

  1. Loss of ovarian function in the VCD mouse-model of menopause leads to insulin resistance and a rapid progression into the metabolic syndrome.

    PubMed

    Romero-Aleshire, Melissa J; Diamond-Stanic, Maggie K; Hasty, Alyssa H; Hoyer, Patricia B; Brooks, Heddwen L

    2009-09-01

    Factors comprising the metabolic syndrome occur with increased incidence in postmenopausal women. To investigate the effects of ovarian failure on the progression of the metabolic syndrome, female B(6)C(3)F(1) mice were treated with 4-vinylcyclohexene diepoxide (VCD) and fed a high-fat (HF) diet for 16 wk. VCD destroys preantral follicles, causing early ovarian failure and is a well-characterized model for the gradual onset of menopause. After 12 wk on a HF diet, VCD-treated mice had developed an impaired glucose tolerance, whereas cycling controls were unaffected [12 wk AUC HF mice 13,455 +/- 643 vs. HF/VCD 17,378 +/- 1140 mg/dl/min, P < 0.05]. After 16 wk on a HF diet, VCD-treated mice had significantly higher fasting insulin levels (HF 5.4 +/- 1.3 vs. HF/VCD 10.1 +/- 1.4 ng/ml, P < 0.05) and were significantly more insulin resistant (HOMA-IR) than cycling controls on a HF diet (HF 56.2 +/- 16.7 vs. HF/VCD 113.1 +/- 19.6 mg/dl x microU/ml, P < 0.05). All mice on a HF diet gained more weight than mice on a standard diet, and weight gain in HF/VCD mice was significantly increased compared with HF cycling controls. Interestingly, even without a HF diet, progression into VCD-induced menopause caused a significant increase in cholesterol and free fatty acids. Furthermore, in mice fed a standard diet (6% fat), insulin resistance developed 4 mo after VCD-induced ovarian failure. Insulin resistance following ovarian failure (menopause) was prevented by estrogen replacement. Studies here demonstrate that ovarian failure (menopause) accelerates progression into the metabolic syndrome and that estrogen replacement prevents the onset of insulin resistance in VCD-treated mice. Thus, the VCD model of menopause provides a physiologically relevant means of studying how sex hormones influence the progression of the metabolic syndrome.

  2. 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.

  3. Expression and redistribution of cellular Bad, Bax, and Bcl-X(L) protein is associated with VCD-induced ovotoxicity in rats.

    PubMed

    Hu, X; Christian, P; Sipes, I G; Hoyer, P B

    2001-11-01

    Previous studies have shown that 4-vinylcyclohexene diepoxide (VCD)-induced ovotoxicity in rats is likely caused by acceleration of the normal rate of atresia (apoptosis). VCD-induced ovotoxicity is specific for small preantral follicles and is associated with increased activity of caspase cascades. The present study was designed to investigate the alteration of expression and distribution of several Bcl-2 family member proteins induced by dosing of VCD in rat small ovarian follicles. Female F344 rats were given a single dose of VCD (80 mg/kg, i.p., 1 day; a time when ovotoxicity is not initiated), or dosed daily for 15 days (80 mg/kg, i.p., 15 days; a time when significant ovotoxicity is underway). Four hours following the final dose, livers and ovaries were collected. Ovarian small (25-100 microm) and large (100-250 microm) preantral follicles were isolated, and subcellular fractions (cytosolic and mitochondrial) were prepared. Compared with controls, levels of the proapoptotic protein, Bad, were greater in both cytosolic and mitochondrial fractions of small preantral follicles collected from 15-day VCD-treated rats (cytosol, 1.97 +/- 0.16; mitochondria, 2.20 +/- 0.24, VCD/control, P < 0.05). After 15 days of daily VCD dosing, total cellular antiapoptotic Bcl-x(L) protein levels were unaffected in small preantral follicles, but its distribution in mitochondrial and cytosolic components was altered (mitochondria, 0.635 +/- 0.08; cytosol, 1.39 +/- 0.14, VCD/control, P < 0.05). Likewise, VCD did not affect protein levels of proapoptotic Bax in small follicles on Day 15. However, consistent with a Bax-mediated mechanism of apoptosis, the relative ratio of Bax/Bcl-x(L) in the mitochondrial fraction of small preantral follicles was significantly increased by VCD dosing (1.62 +/- 0.21, VCD/control, P < 0.05). Immunofluorescence staining intensity evaluated by confocal microscopy visualized cytochrome c protein in the cytosolic compartment in granulosa cells of preantral

  4. Hormonal status affects the progression of STZ-induced diabetes and diabetic renal damage in the VCD mouse model of menopause.

    PubMed

    Keck, Maggie; Romero-Aleshire, Melissa J; Cai, Qi; Hoyer, Patricia B; Brooks, Heddwen L

    2007-07-01

    Changes in the estrogen/testosterone balance at menopause may negatively influence the development of diabetic kidney disease. Furthermore, recent studies suggest that changes in hormone levels during perimenopause may influence disease development. Injection of 4-vinylcyclohexene diepoxide (VCD) in B(6)C(3)F(1) mice induces gradual ovarian failure, preserving both the perimenopausal (peri-ovarian failure) and menopausal (post-ovarian failure) periods. To address the impact of the transition into menopause on the development of diabetes and diabetic kidney damage, we used streptozotocin (STZ)-induced diabetes in the VCD model of menopause. After 6 wk of STZ-induced diabetes, blood glucose was significantly increased in post-ovarian failure (post-OF) diabetic mice compared with cycling diabetic mice. In peri-ovarian failure (peri-OF) diabetic mice, blood glucose levels trended higher but were not significantly different from cycling diabetic mice, suggesting a continuum of worsening blood glucose across the menopausal transition. Cell proliferation, an early marker of damage in the kidney, was increased in post-OF diabetic mice compared with cycling diabetic mice, as measured by PCNA immunohistochemistry. In post-OF diabetic mice, mRNA abundance of early growth response-1 (Egr-1), collagen-4alpha1, and matrix metalloproteinase-9 were increased and 3beta-hydroxysteroid dehydrogenase 4 (3beta-HSD4) and transforming growth factor-beta(2) (TGF-beta(2)) were decreased compared with cycling diabetic mice. In peri-OF diabetic mice, mRNA abundance of Egr-1 and 3beta-HSD4 were increased, and TGF-beta(2) was decreased compared with cycling diabetic mice. This study highlights the importance and utility of the VCD model of menopause, as it provides a physiologically relevant system for determining the impact of the menopausal transition on diabetes and diabetic kidney damage.

  5. Isomerization of 4-vinylcyclohexene radical cation. A tandem mass spectrometry study

    SciTech Connect

    Vollmer, D.; Rempel, D.L.; Gross, M. L. ); Williams, F. )

    1995-02-08

    Investigation by matrix-isolation ESR has shown that 4-vinylcyclohexene, 1, surprisingly undergoes isomerization to the bicyclo[3.2.1]oct-2-ene ion, 3. Here we demonstrate the occurrence of this isomerization in the gas phase by use of tandem (MS/MS) sector and Fourier transform (FT) mass spectrometries. The radical cations of 4-vinylcyclohexene (IE = 8.93 eV) or bicyclo[3.2.1]oct-2-ene (approximately 14 kcal/mol more stable than that of 4-vinylcyclohexene) were formed, in separate trials, in a chemical ionization (CI) source by electron ionization (EI). The radical cations were then studied by obtaining their collisionally activated decomposition (CAD) spectra. The CAD spectra are similar, indicating that the isomerization has occurred. Both the sector and the FT mass spectrometer results reflect those obtained in the matrix-isolation ESR investigation. That is isomerizes to 3 at high internal energy, but is stable at low internal energy. Two mechanisms explain this rearrangement. The second mechanism is questionable because the most stable olefin radical cation formed from 5 is that of bicyclo[2.2.2]-2-octene, which gives different ESR and CAD spectra than those of 1 or 3. The CAD spectrum of bicyclo[2.2.2]-2-octene radical cation indicates that the retro-Diels-Alder loss of ethylene is more facile than that from 1 or 3. 18 refs., 3 figs.

  6. 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.

  7. 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.

  8. What Is Vocal Cord Dysfunction (VCD)?

    MedlinePlus

    ... from asthma, VCD, or both at the same time. Am J Respir Crit Care Med Vol. 180, P5-P6, 2009. Online Version Updated September 2013 ATS Patient Education Series © 2009 American Thoracic Society www.thoracic.org ATS ...

  9. Alkyltransferase-mediated Toxicity of 1,3-Butadiene Diepoxide

    PubMed Central

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

    2008-01-01

    Human O6-alkylguanine-DNA alkyltransferase (hAGT) expression increases mutations and cytotoxicity following exposure to 1,3-butadiene diepoxide (BDO) and hAGT-DNA cross-links are formed in the presence of BDO. We have used hAGT mutants to investigate the mechanism of cross-link formation and genotoxicity. Formation of a hAGT-DNA conjugate in vitro was observed with C145S and C145A mutant proteins but was considerably diminished with the C145A/C150S double mutant confirming that cross-linking primarily involves either of these two cysteine residues, which are located in the active site pocket of the protein. Cross-link formation by BDO occurred both via (a) an initial reaction of BDO with hAGT followed by attack of the reactive hAGT complex on DNA, and (b) the initial reaction of BDO with DNA followed by a reaction between hAGT and the DNA adduct. These results differ from those with 1,2-dibromoethane (DBE) where Cys145 is the only site of attachment and pathway (b) does not occur. The complex formed between hAGT at Cys145 and BDO was very unstable in aqueous solution. However, the BDO-hAGT complex at Cys150 exhibited stability for more than 1 h. The effect of hAGT and mutants on BDO-induced genotoxicity was studied in E. coli using the forward assay to rifampicin resistance. Both mutations and cell killing were greatly increased by wild type hAGT and there was a smaller but significant effect with the C145A mutant. The R128A mutant and R128A/C145A and C145A/C150S double mutants were ineffective supporting the hypothesis that the formation of hAGT-DNA cross-links is responsible for the enhanced genotoxicity detected in this biological system. In the absence of hAGT, there were equal proportions of G:C to A:T transitions, G:C to T:A transversions and A:T to T:A transversions. Wild type hAGT expression yielded significantly greater G:C to A:T and A:T to G:C transitions, whereas C145A mutant expression resulted in more transitions and transversions at A:T base

  10. On the complementarity of ECD and VCD techniques.

    PubMed

    Nicu, Valentin Paul; Mándi, Attila; Kurtán, Tibor; Polavarapu, Prasad L

    2014-09-01

    An unprecedented complementarity of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectroscopic techniques is demonstrated by showing that each technique reveals the structure of a different molecular segment. Using a flexible molecule of biological significance we show that the synergetic use of ECD and VCD yields more complete structural characterization as it provides improved and more reliable conformer resolution.

  11. Thoughts on VCD-145 Detector Calibration

    SciTech Connect

    Morgan, W V

    2005-02-10

    In 1980, Don Smith requested that the EG&G Detector Group in North Las Vegas provide a summary of calibrated sensitivities for the VCD-145 detector. The &sired information was provided in a memorandum from Sam Egdorf (Reference 1). A memo from Brent Davis issued a week later described the effect on VCD-145 detector sensitivity that resulted from changing the thickness of the stainless steel entrance window (Reference 2). This memo is intended first to effectively archive those two references, and second to record thoughts about the significance of their contents. Reference 1 lists a total of 118 calibrated values for 80 different VCD-145 detectors, from 1977 to 1980. With only four exceptions, all of the serial numbers from V004 to V087 were included. The earlier calibrations were for detectors with 1-mil entrance windows, and the later ones were for detectors with 2-mil entrance windows. Three of the earlier units were calibrated at both thicknesses by temporarily placing an extra 1-mil sheet of stainless steel across the window. Altogether six different collimator diameters were used, from 60 mm to 95 mm. Some units were calibrated for more than one collimator diameter, and 14 were at some point designated as backup detectors for a second event. Reference 2 describes the effect of window thickness on calibrated sensitivity. Quoting that reference: ''To demonstrate that the sensitivity decrease is solely a function of the window thickness, a standard VCD-145 detector with a 0.001-inch thick window was calibrated with the {sup 60}Co source. Then without changing detector or geometry, a 0.001 -inch thick stainless steel foil (same material as that of the window) was placed directly in front of the detector window, effectively making a 0.002-inch thick entrance window. The detector was again calibrated. This technique was repeated until the detector had an entrance window equivalent to 0.010-inches thick.'' There are multiple reasons to suspect that the accuracy of

  12. 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

  13. 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

  14. VCD studies on chiral characters of metal complex oligomers.

    PubMed

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-07

    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.

  15. 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.

  16. 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

    2016-08-03

    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.

  17. 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.

  18. Vibrational CD (VCD) and atomic force microscopy (AFM) study of DNA interaction with Cr3+ ions: VCD and AFM evidence of DNA condensation.

    PubMed

    Andrushchenko, V; Leonenko, Z; Cramb, D; van de Sande, H; Wieser, H

    The interaction of natural calf thymus DNA with Cr(3+) ions was studied at room temperature by means of vibrational CD (VCD) and infrared absorption (ir) spectroscopy, and atomic force microscopy (AFM). Cr(3+) ion binding mainly to N(7) (G) and to phosphate groups was demonstrated. Psi-type VCD spectra resembling electronic CD (ECD) spectra, which appear during psi-type DNA condensation, were observed. These spectra are characterized mainly by an anomalous, severalfold increase of VCD intensity. Such anomalous VCD spectra were assigned to DNA condensation with formation of large and dense particles of a size comparable to the wavelength of the probing ir beam and possessing large-scale helicity. Atomic force microscopy confirmed DNA condensation by Cr(3+) ions and the formation of tight DNA particles responsible for the psi-type VCD spectra. Upon increasing the Cr(3+) ion concentration the shape of the condensates changed from loose flower-like structures to highly packed dense spheres. No DNA denaturation was seen even at the highest concentration of Cr(3+) ions studied. The secondary structure of DNA remained in a B-form before and after the condensation. VCD and ir as well as AFM proved to be an effective combination for investigating DNA condensation. In addition to the ability of VCD to determine DNA condensation, VCD and ir can in the same experiment provide unambiguous information about the secondary structure of DNA contained in the condensed particles.

  19. 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.

  20. Enhancement of IR and VCD intensities due to charge transfer.

    PubMed

    Nicu, Valentin Paul; Autschbach, Jochen; Baerends, Evert Jan

    2009-03-14

    Donor-acceptor interactions such as the one between the Cl(-) base and the N-H sigma* acceptor orbitals encountered in the complexation of Cl(-) counterions to the [Co(en)(3)](3+) transition metal complex, have been shown to cause huge enhancement (between 1 and 2 orders of magnitude) of the VCD intensities of N-H stretching modes. This effect has been fully analyzed, and could be attributed to increased charge flow from the Cl(-) donors when the N-H bonds become stretched. The transfer of charge counteracts the movement of negative electronic charge that happens along with the motion of the H nuclei, effectively reversing the electronic part of the electric dipole transition moment (EDTM) in the direction of the charge flow (z, say), and of the magnetic transition dipole moment (MDTM) in the perpendicular direction. The consequences for the IR and VCD intensity follow: IR intensity is strongly increased if the EDTM is polarized in the z direction, e.g. in A(2) modes, but not so much if it is polarized in the xy plane (E modes), the VCD is strongly enhanced if the EDTM and MTDM are polarized in the xy plane (in E modes), but less so when they are polarized in the z direction (in A(2) modes). The explanation holds generally for complexation phenomena of this sort, including the donor-acceptor part of hydrogen bonding interactions, e.g. with solvent molecules.

  1. Vibrational Circular Dichroism (VCD) Reveals Subtle Conformational Aspects and Intermolecular Interactions in the Carnitine Family.

    PubMed

    Mazzeo, Giuseppe; Abbate, Sergio; Longhi, Giovanna; Castiglioni, Ettore; Villani, Claudio

    2015-12-01

    Vibrational circular dichroism spectra (VCD) in the mid-IR region and electronic circular dichroism (ECD) spectra for three carnitine derivatives in the form of hydrochloride salts were recorded in deuterated methanol solutions. Density Functional Theory calculations help one to understand the significance of the observed VCD bands. VCD and ECD spectra are informative about the absolute configuration of the molecule, but VCD data reveal also some conformational aspects in the N,N,N-trimethyl moiety and inform us about intermolecular interactions gained from the carbonyl stretching region for the acyl substituted carnitines.

  2. NIR-VCD, vibrational circular dichroism in the near-infrared: experiments, theory and calculations.

    PubMed

    Abbate, Sergio; Castiglioni, Ettore; Gangemi, Fabrizio; Gangemi, Roberto; Longhi, Giovanna

    2009-01-01

    The first well documented experiments of Near Infrared Vibrational Circular Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history of NIR-VCD, encompassing both instrumental development and theoretical/computational methods that allow interpretation of experimental spectra, harvesting useful structural information therefrom. We hope to stimulate interest in this still scarcely explored spectroscopy of chiral molecules.

  3. 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.

  4. Solvent effects on IR and VCD spectra of natural products: an experimental and theoretical VCD study of pulegone.

    PubMed

    Debie, Elke; Bultinck, Patrick; Herrebout, Wouter; van der Veken, Benjamin

    2008-06-28

    The VCD spectra of pulegone, dissolved in CDCl3, CD2Cl2 and CS2 have been recorded in the frequency range from 1000 to 3000 cm(-1). The assignment of the absolute configuration was performed by comparing the experimental data with theoretical spectra computed at the B3LYP/6-311+G(d,p) level. Analysis of the agreement in several spectral regions revealed significant shortcomings when comparing with vacuum calculations. It is shown that the agreement improves when the solvent effects are taken into account by a continuum model. For the measurements in CDCl3 and CD2Cl2 further improvement was found when considering explicitly 1 : 1 complexes between a pulegone and a CDCl3 or CD2Cl2 solvent molecule in vacuo, while the best agreement was obtained when embedding these in a continuum model. The presence of the chiral solute was found to induce a VCD active C-D stretch band which could be modeled also at ab initio level.

  5. Comparison of vibrational circular dichroism instruments: development of a new dispersive VCD.

    PubMed

    Lakhani, Ahmed; Malon, Petr; Keiderling, Timothy A

    2009-07-01

    A dispersive vibrational circular dichroism (VCD) instrument has been designed and optimized for the measurement of mid-infrared (MIR) bands such as the amide I and amide II vibrational modes of peptides and proteins. The major design considerations were to construct a compact VCD instrument for biological molecules, to increase signal-to-noise (S/N) ratio, to simultaneously collect and digitize the sample transmission and polarization modulation signals, and to digitally ratio them to yield a VCD spectrum. These were realized by assembling new components using design factors adapted from previous VCD instruments. A collection of spectra for peptides and proteins having different dominant secondary structures (alpha-helix, beta-sheet, and random coil) measured for identical samples under the same conditions showed that the new instrument had substantially improved S/N as compared with our previous dispersive VCD instrument. These instruments both provide protein VCD for the amide I that are comparable to or somewhat better than those measurable with commercial Fourier transform (FT) VCD instruments if just the amide I band in the spectra is obtained at modest resolution (8 cm(-1)) with the same total data collection time on each type of instrument.

  6. The determination of the absolute configurations of chiral molecules using vibrational circular dichroism (VCD) spectroscopy.

    PubMed

    Stephens, Philip J; Devlin, Frank J; Pan, Jian-Jung

    2008-05-15

    The vibrational circular dichroism (VCD) spectra of the two enantiomers of a chiral molecule are of equal magnitude and opposite sign: i.e. mirror-image enantiomers give mirror-image VCD spectra. In principle, the absolute configuration (AC) of a chiral molecule can therefore be determined from its VCD spectrum. In practice, the determination of the AC of a chiral molecule from its experimental VCD spectrum requires a methodology which reliably predicts the VCD spectra of its enantiomers. The only reliable methodology developed to date uses the Stephens quantum-mechanical theory of the rotational strengths of fundamental vibrational transitions, developed in the early 1980s, implemented using ab initio density functional theory in the GAUSSIAN program in the mid 1990s. This methodology has by now been widely used in determining ACs from experimental VCD spectra. In this article we discuss the protocol for determining the ACs of chiral molecules with optimum reliability and its implementation for a variety of molecules, including the D3 symmetry perhydrotriphenylene, a thiazino-oxadiazolone recently shown to be a highly active calcium entry channel blocker, the alkaloid natural products schizozygine, iso-schizogaline, and iso-schizogamine, and the iridoid natural products plumericin, iso-plumericin, and prismatomerin. The power of VCD spectroscopy in determining ACs, even for large organic molecules and for substantially conformationally-flexible organic molecules is clearly documented.

  7. Evidence of dihydrogen bonding of a chiral amine-borane complex in solution by VCD spectroscopy.

    PubMed

    Merten, Christian; Berger, Christopher J; McDonald, Robert; Xu, Yunjie

    2014-09-08

    IR and vibrational circular dichroism (VCD) spectra of a chiral amine-borane in solution are investigated. By comparison of experimental and calculated spectra, unique VCD spectral signatures, which can be attributed to the formation of dihydrogen-bonded dimers in solution, are identified for the first time. These VCD features are highly sensitive to the specific dihydrogen-bonding topologies utilized by the chiral amine-borane subunits and thus provide direct structural information of these dihydrogen-bonded species in solution. Differences in the dihydrogen binding arrangements in solution and in solid state are also revealed.

  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. Intermolecular Interactions of a Chiral Amine Borane Adduct Revealed by VCD Spectroscopy.

    PubMed

    Osowski, Tobias; Golbek, Julia; Merz, Klaus; Merten, Christian

    2016-06-23

    Amine boranes feature strong hydrogen bonding acceptor and donor moieties in close proximity, leading, for instance, to dihydrogen bonding driven self-aggregation. In this work, the infrared (IR) and vibrational circular dichroism (VCD) spectra of the bulky bis(α-phenylethyl)amine borane 1 in chloroform and acetonitrile solution are reported. By comparison with calculated spectra, the VCD spectral features observed in chloroform solution can clearly be associated with the presence of monomeric species. A shift of the conformational preferences occurs when changing the solvent to acetonitrile, which can only be deduced from the VCD spectral signatures but not from the IR spectrum. Using variable-temperature IR and VCD spectroscopy, the dihydrogen bonded dimeric species is characterized experimentally at -50 °C and theoretically by means of density functional theory calculations.

  10. VCD to determine absolute configuration of natural product molecules: secolignans from Peperomia blanda.

    PubMed

    Felippe, Lidiane G; Batista, João M; Baldoqui, Debora C; Nascimento, Isabele R; Kato, Massuo J; He, Yanan; Nafie, Laurence A; Furlan, Maysa

    2012-06-07

    The absolute configuration and solution-state conformers of three peperomin-type secolignans isolated from Peperomia blanda (Piperaceae) are unambiguously determined by using vibrational circular dichroism (VCD) spectroscopy associated with density functional theory (DFT) calculations. Advantages of VCD over the electronic form of CD for the analysis of diastereomers are also discussed. This work extends our growing knowledge about secondary metabolites within the Piperaceae family species while providing a definitive and straightforward method to assess the absolute stereochemistry of secolignans.

  11. Determination of f+π (0) or extraction of |Vcd | from semileptonic D decays

    NASA Astrophysics Data System (ADS)

    Rong, G.; Fang, Y.; Ma, H. L.; Zhao, J. Y.

    2015-04-01

    By globally analyzing all existing measured branching fractions for D → πe+νe decays, partial decay rates in different four-momentum transfer-squared q2 bins, as well as products of the decay form factor f+π (q2) and the Cabibbo-Kobayashi-Maskawa (CKM) quark-mixing matrix element |Vcd |, we obtain f+π (0) |Vcd | = 0.1428 ±0.0019-0.0011+0.0019. This product, in conjunction with the |Vus | determined from (semi-)leptonic K decays and the relation of |Vcd | = |Vus | = λ from the unitarity of the CKM matrix, implies a value for the D → π semileptonic form factor f+π (0) =0.634-0.010+0.012 ± 0.002, which is consistent within error with those calculated in theory based on quantum chromodynamics (QCD). Alternately, using this product together with the most accurate form factor calculated in Lattice QCD (LQCD), we find |Vcd| D → πe+νe =0.2144-0.0033+0.0040 ± 0.0093. Combining this |Vcd| D → πe+νe with |Vcd| D+ →μ+νμ = 0.2160 ± 0.0049 ± 0.0014 extracted from both the BESIII and CLEO-c measurements of D+ →μ+νμ decays, we find the most precisely extracted |Vcd | to be |Vcd | = 0.2157 ± 0.0045 up to date. From these determined quantities we find [mD+ f+π (0) /fD+ ] exp = 5.81 ± 0.17, which is in excellent agreement with [mD+ f+π (0) /fD+ ] LQCD = 5.85 ± 0.26 calculated in LQCD, indicating that the LQCD approach to the charm quark sector is excellent. Using this |Vcd | together with the PDG'2014 |Vud | and |Vtd |, we check for the first column unitarity and find |Vud|2 + |Vcd|2 + |Vtd|2 - 1 = - 0.004 ± 0.002, which deviates from unitarity by 2σ.

  12. Determination of the absolute configuration of the natural product Klaivanolide via density functional calculations of vibrational circular dichroism (VCD).

    PubMed

    Devlin, Frank J; Stephens, Philip J; Figadère, Bruno

    2009-01-01

    The absolute configuration (AC) of the antiprotozoal lactone, Klaivanolide, 1, from Uvaria klaineana, has been determined using Vibrational Circular Dichroism (VCD) spectroscopy. The experimental VCD spectrum of the (+) enantiomer of 1 was measured. To analyze the AC of (+)-1, the conformationally-averaged VCD spectrum of 7-S-1 was calculated using density functional theory (DFT) and the GAUSSIAN 03 program. The B3PW91/TZ2P conformationally-averaged VCD spectrum of 7-S-1 proves that the AC of 1 is 7-S-(+).

  13. Raloxifene protects against seizures and neurodegeneration in a mouse model mimicking epilepsy in postmenopausal woman.

    PubMed

    Pottoo, F H; Bhowmik, M; Vohora, D

    2014-12-18

    Epilepsy in menopausal women presents several challenges in the treatment including an increased risk of seizures due to hormone replacement therapy. We investigated the hypothesis if raloxifene, a selective oestrogen receptor modulator, could be employed to prevent behavioural seizures and morphological alterations in a mouse model mimicking epilepsy in postmenopausal women. Female mice were made ovotoxic by treatment with 4-vinylcyclohexene diepoxide (VCD) to mimic a postmenopausal state. They were then subjected to kainic acid (KA)-induced seizures and neurotoxicity, as assessed by microscopic examination of hippocampus, relevant to human temporal lobe epilepsy. VCD administration (for 15days followed by a drug-free period of 30days) induced ovotoxicity in mice as evidenced by reduced number of primary ovarian follicles. This was accompanied by a 62.4% reduction in serum oestradiol levels. The bone mineral density of ovotoxic mice, however, remained unaffected. Raloxifene (8mg/kg) reduced the seizure severity score in both normal and ovotoxic mice and protected against degeneration induced by KA in the CA3, CA1 sub-fields and hilus of the DG. Hippocampal TGF-β3 levels were not affected by any of the treatments. We show the potential protective role of raloxifene in preventing seizures and neuronal damage in a mouse model mimicking epilepsy in postmenopausal women which was found unrelated to hippocampal TGF-β3. Raloxifene might represent a novel therapeutic option for postmenopausal temporal lobe epileptic woman.

  14. Conformational studies on chiral rhodium complexes by ECD and VCD spectroscopy.

    PubMed

    Szilvágyi, Gábor; Majer, Zsuzsa; Vass, Elemér; Hollósi, Miklós

    2011-04-01

    This article reports vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectroscopic studies in acetonitrile on the chiral Rh(2)(O-Phe-Cbz)(1)(OAc)(3) and Rh(2)(O-Phe-Ac)(1)(OAc)(3) complexes (abbreviated Rh(2)Z(1) and Rh(2)Ac(1) , respectively; Phe, L-phenylalanine; Cbz, benzyloxycarbonyl; Ac, acetyl) supported by theoretical calculations. The ECD spectra of the complexes depend on temperature that indicates the conformational mobility of the chiral ligands. Calculations of the VCD spectra were performed at ab initio (DFT) level of theory using Gaussian 03 [B3LYP functional combined with the LANL2DZ basis set for the dirhodium core and the 6-31G(d) basis set for other atoms]. The population-weighted sums of the computed VCD spectra of the conformers are in excellent agreement with the experimental VCD spectra. The combination of the VCD and ECD spectroscopic methods led us to the structural characterization of the complexes.

  15. Assignment of absolute configurations of highly flexible linear diterpenes from the brown alga Bifurcaria bifurcata by VCD spectroscopy.

    PubMed

    Merten, Christian; Smyrniotopoulos, Vangelis; Tasdemir, Deniz

    2015-11-21

    Correct assignment of the stereogenic centers of highly flexible linear diterpenes (LDs) is challenging. Herein we report the first application of VCD spectroscopy for the absolute configuration determination of LDs of algal origin and provide experimental and computational procedures, such as a fragmentation approach, which will facilitate the use of VCD spectroscopy for configuration assignments of LDs.

  16. 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.

  17. Conformational study of chiral penicillamine ligand on optically active silver nanoclusters with IR and VCD spectroscopy

    NASA Astrophysics Data System (ADS)

    Yao, Hiroshi; Nishida, Naoki; Kimura, Keisaku

    2010-02-01

    The conformation of chiral D-/ L-penicillamine ( D-/ L-Pen) adsorbed on optically active silver nanoclusters with a mean core diameter of about 1.1 nm was investigated by infrared (IR) and vibrational circular dichroism (VCD) spectroscopy. IR spectra of the D-/ L-Pen-protected nanoclusters in D 2O/CD 3OD solution are essentially identical, but the VCD exhibits a mirror image relationship indicating that these species have enantiomeric relationship. The experimental IR and VCD spectra are compared with the calculated ones for different model conformers at the DFT/B3PW91 level. The analysis in the spectral region of ν asym(COO -) and δ sym(NH 2) modes reveals significant shortcomings when comparing with vacuum calculations. We then take a bulk solvent effect into account in the theoretical calculations to obtain better agreement, resulting in the establishment of a preferential conformation of chiral penicillamine on the silver nanocluster surface.

  18. IR-Raman-VCD study of R-(+)-pulegone: influence of the solvent.

    PubMed

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

    2011-08-15

    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.

  19. VCD study of alpha-methylbenzyl amine derivatives: detection of the unchanged chiral motif.

    PubMed

    Merten, Christian; Amkreutz, Marc; Hartwig, Andreas

    2010-08-01

    Chiral alpha-methylbenzyl amine is a well known and often used chiral auxiliary, e.g., in the resolution of racemates or asymmetric catalysis. In this work, alpha-methylbenzyl amine and its derivatives N,alpha-dimethylbenzyl amine, N,N,alpha-trimethylbenzyl amine, and bis[alpha-methylbenzyl] amine were investigated by vibrational circular dichroism (VCD) spectroscopy and density functional theory (DFT). For all compounds, stable low energy conformers were obtained by the DFT calculations and based on those, the theoretical vibrational absorption (VA) and VCD spectra were calculated and compared with experimental spectra. Hence, the absolute configurations and conformational preferences were determined. A qualitative comparison of all the experimental VCD spectra of the investigated chiral molecules supported by the calculated ones is given which clearly shows similarities between the spectra of the different chiral amines. These can be assigned to vibrations of the unchanged chiral center.

  20. Cognitive changes across the menopause transition: A longitudinal evaluation of the impact of age and ovarian status on spatial memory.

    PubMed

    Koebele, Stephanie V; Mennenga, Sarah E; Hiroi, Ryoko; Quihuis, Alicia M; Hewitt, Lauren T; Poisson, Mallori L; George, Christina; Mayer, Loretta P; Dyer, Cheryl A; Aiken, Leona S; Demers, Laurence M; Carson, Catherine; Bimonte-Nelson, Heather A

    2017-01-01

    Cognitive changes that occur during mid-life and beyond are linked to both aging and the menopause transition. Studies in women suggest that the age at menopause onset can impact cognitive status later in life; yet, little is known about memory changes that occur during the transitional period to the postmenopausal state. The 4-vinylcyclohexene diepoxide (VCD) model simulates transitional menopause in rodents by depleting the immature ovarian follicle reserve and allowing animals to retain their follicle-deplete ovarian tissue, resulting in a profile similar to the majority of perimenopausal women. Here, Vehicle or VCD treatment was administered to ovary-intact adult and middle-aged Fischer-344 rats to assess the trajectory of cognitive change across time with normal aging and aging with transitional menopause via VCD-induced follicular depletion, as well as to evaluate whether age at the onset of follicular depletion plays a role in cognitive outcomes. Animals experiencing the onset of menopause at a younger age exhibited impaired spatial memory early in the transition to a follicle-deplete state. Additionally, at the mid- and post- follicular depletion time points, VCD-induced follicular depletion amplified an age effect on memory. Overall, these findings suggest that age at the onset of menopause is a critical parameter to consider when evaluating learning and memory across the transition to reproductive senescence. From a translational perspective, this study illustrates how age at menopause onset might impact cognition in menopausal women, and provides insight into time points to explore for the window of opportunity for hormone therapy during the menopause transition period. Hormone therapy during this critical juncture might be especially efficacious at attenuating age- and menopause- related cognitive decline, producing healthy brain aging profiles in women who retain their ovaries throughout their lifespan.

  1. Effects of dehydroepiandrosterone (DHEA) on follicular dynamics in a diminished ovarian reserve in vivo model.

    PubMed

    Hassa, Hikmet; Aydin, Yunus; Ozatik, Orhan; Erol, Kevser; Ozatik, Yasemin

    2015-06-01

    The objective of this study was to determine whether there are changes in primary, primordial, and growing follicles after dehydroepiandrosterone (DHEA) administration in rats that have diminished ovarian reserve (DOR) due to 4-vinylcyclohexene diepoxide (VCD) application, and to examine the mechanism of the probable effect of DHEA on folliculogenesis. Two groups of Wistar rats were used. In Group A unilateral oophorectomy (eight rats) was carried out on day-0. The remaining study ovary was removed by relaparotomy after VCD (160 mg/kg, intraperitoneally) was administered for 15 days. In Group B unilateral oophorectomy (eight rats) was carried out on day-0. The remaining study ovary was removed by relaparotomy after VCD (160 mg/kg, intraperitoneally) administration for 15 days followed by DHEA (60 mg/kg body weight) daily for 45 days. Primordial, primary, and growing (secondary+antral) follicles were counted in 1,664 sections from 32 ovaries. In all three types of follicles (primordial, primary, and growing), the number of follicles significantly decreased in the study ovaries compared to the control ovaries in both Group A and Group B. In Group B, atresia rates were significantly lower in the study ovary compared to the control ovary in all of the follicular groups: primordial (p=0.02), primary (p=0.01), and growing (p=.027). To demonstrate the probable effects of DHEA on follicular dynamics, we also compared the study ovaries in both groups; the primordial (p=0.027), primary (p=0.031), and growing (p=0.04) number of follicles were significantly higher in Group B compared to Group A. In conclusion, our findings suggest that DHEA administration in DOR rats due to VCD results in a larger follicular pool. Decreased atresia may be one of the possible effects of DHEA in DOR cases. Whatever the mechanism, DHEA treatment potentially may be useful clinically as a means to increase the number of gonadotropin-responsive follicles for ovarian stimulation.

  2. Dirhodium complexes: determination of absolute configuration by the exciton chirality method using VCD spectroscopy.

    PubMed

    Szilvágyi, Gábor; Brém, Balázs; Báti, Gábor; Tölgyesi, László; Hollósi, Miklós; Vass, Elemér

    2013-09-28

    Inherently chiral dinuclear rhodium complexes have been synthesized from the well-known dirhodium(II)-acetate and chiral/achiral amino acids. These complexes have a twisted paddlewheel structure due to axial chirality. Chiral induction could be observed when the ligands were chiral, opposite to the case of achiral ligands, where a racemic mixture was formed. The racemic mixture was separated by chiral HPLC-ECD. The stereochemical properties of these complexes were determined by VCD spectroscopy supported by theoretical calculations at the DFT level. We present a simple route to determine the absolute configuration by an exciton chirality method using VCD spectroscopy.

  3. Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers.

    PubMed

    Zinna, Francesco; Pescitelli, Gennaro

    2016-02-01

    Three alkyl vinylethers from our collection of chiral samples were investigated through VCD spectroscopy, in combination with Density Functional Theory (DFT) calculations. Despite the simplicity of the compounds, reproducing all the spectral features is an involved task, since the many significantly populated conformers contribute to the total VCD spectrum with bands which often have opposite signatures. Nevertheless, we show that certain bands can be satisfactorily reproduced by calculation and therefore they may be employed for the determination of absolute configuration in these and similar compounds, for which no simple alternative method is available.

  4. 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

    2016-08-03

    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.

  5. 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

    2015-06-07

    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.

  6. Prediction of (L)-methionine VCD spectra in the gas phase and water solution.

    PubMed

    Rode, Joanna E; Dobrowolski, Jan Cz; Sadlej, Joanna

    2013-11-21

    In this paper we provide a computational study of the l-methionine conformational landscape and VCD spectra in the gas phase and a water environment simulated by implicit PCM and the hybrid model, i.e., a combination of explicit "microsolvation" and implicit models. In the gas phase, two groups of conformers differing in H-bonding, i.e., OH···NH2 and NH···O═C, could be distinguished based solely on the IR ν(OH) and ν(NH) stretching vibrations range. On the other hand, VCD better reflected chain differences. The most stable OH···NH2 conformer was predicted to be easily detected, and the presence of two out of four NH···O═C conformers could be confirmed. Three zwitterionic methionine conformers were shown to dominate in water. Their VCD spectra, simulated within the hybrid model at the B3LYP-IEF-PCM/aug-cc-pVDZ level of theory, indicated that they could be recognized in the mixture. Use of the hybrid model is crucial for good reproduction of the hydrogen bonding pattern in the VCD spectra of methionine in water solution. However, the 1300-800 cm(-1) region of the skeleton vibrations of methionine appeared to be relatively insensitive to the model of the solvent.

  7. 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.

  8. A VCD robust mode analysis of induced chirality: the case of pulegone in chloroform.

    PubMed

    Nicu, Valentin Paul; Debie, Elke; Herrebout, Wouter; Van der Veken, Benjamin; Bultinck, Patrick; Baerends, Evert Jan

    2009-01-01

    Vibrational modes in an achiral molecule may acquire rotational strength by complexation to a chiral molecule, as happens for achiral solvent molecules complexed to a chiral solute. We investigate this transfer of chirality in vibrational circular dichroism for the pulegone molecule in CDCl(3) solvent from the point of view of the robustness concept introduced recently. It turns out that the transfer of chirality yields nonrobust modes, which means that, although they are observed in vibrational circular dichroism (VCD) experiments, the sign of these modes cannot be predicted reliably with standard (Density Functional Theory) VCD calculations. This limits the usefulness of the induced chirality phenomenon for obtaining information on the intermolecular interactions that give rise to it.

  9. Speech Therapy Telepractice for Vocal Cord Dysfunction (VCD): MaineCare (Medicaid) Cost Savings.

    PubMed

    Towey, Michael P

    2012-01-01

    This Brief Communication represents an analysis of the cost savings to MaineCare (also referred to as Medicaid) directly attributable to service provided via speech therapy telepractice. Seven female (primarily adolescent) MaineCare patients consecutively referred to Waldo County General Hospital (WCGH) with suspected diagnosis of Vocal Cord Dysfunction (VCD) were treated by speech therapy telepractice. Outcome data demonstrated a first month cost savings of $2376.72. The analysis additionally projected thousands of dollars of potential savings each month in reduced medical costs for this patient group as a result of successful treatment via speech therapy telepractice. The study suggests that without access to speech therapy telepractice for patients with VCD, the medical costs to MaineCare will be ongoing and significant.

  10. Conformational distortion of α-phenylethyl amine in cryogenic matrices - a matrix isolation VCD study.

    PubMed

    Pollok, Corina H; Merten, Christian

    2016-05-21

    The chiral amine α-phenylethyl amine (PEA) was isolated in cryogenic matrices and investigated using vibrational circular dichroism (VCD) and infrared spectroscopy. The potential energy surface (PES) of PEA features five different conformers connected by relatively low conformational transition states. Based on the IR spectra, it could be confirmed that all conformational energy barriers are passed at a deposition temperature of 20 K, and that only the global minimum conformation of PEA is populated in both argon and nitrogen matrices. However, differences in the calculated and experimental VCD spectra indicate deviations from the minimum structure by perturbation of the phenyl ring as well as of the amine orientation. The degree of the perturbation is found to also depend on the choice of the host gas, which shows the subtle influence of the environment on the conformational distortion of PEA.

  11. Design of a new method of antipiracy for VCD/DVD player

    NASA Astrophysics Data System (ADS)

    Li, Hexiong; Xu, Duanyi

    2002-09-01

    In order to protect important content, such as the latest Hollywood movies, a new method of anti-piracy technology -- Embedded copy protection ASIC controlling scheme has been developed. The contents on the disk have been scrambled. Before the content playing, the VCD/DVD Player with embedded copy protection ASIC will detect the disk and need user inputs a license code. If the code matches the embedded ASIC key scheme, the disk will play, or the disk will be rejected.

  12. VCD spectroscopic and molecular dynamics analysis of the Trp-cage miniprotein TC5b.

    PubMed

    Copps, Jeffrey; Murphy, Richard F; Lovas, Sándor

    2007-01-01

    TC5b is a 20 residue polypeptide notable for its compact tertiary structure, a rarity for a short peptide. This structure is due to the "Trp-cage" motif, an association of aromatic, Pro, and Gly residues. The structure of TC5b has been fully characterized by NMR and electronic circular dichroism (ECD) studies, but has never been studied with vibrational circular dichroism (VCD) spectroscopy, which may reveal finer structure. In this study, we examine the VCD spectra of TC5b to characterize the spectroscopic signature of the peptide and its comprising structural elements. TC5b exhibited a negative-positive-negative triplet which is associated with alpha-helical structure in deuterated solvents but also signs of a polyproline II (PPII) helix in the amide I' region. Detection of this element was complicated by the aforementioned triplet form, as well as by an upfrequency shift in PPII helical elements due to the use of the deuterated organic solvents DMSO-d(6) and TFE-d(1). Nevertheless, while ECD spectra showed only alpha-helical structure for TC5b, VCD spectroscopy revealed a more complex structure which was in agreement with NMR results. VCD spectroscopy also showed a rapid conformational change of the peptide at temperatures above 35 degrees C in D(2)O and in aqueous solvent with greater than 75% DMSO-d(6) content. Molecular dynamics (MD) simulations to investigate this latter effect of DMSO-d(6) on TC5b were conducted in DMSO and 50% (v/v) DMSO in H(2)O. In DMSO unfolding of the peptide was rapid while in 50% (v/v) DMSO in H(2)O the unfolding was more gradual.

  13. Conformational studies of Phe-rich foldamers by VCD spectroscopy and ab initio calculations.

    PubMed

    Longhi, Giovanna; Abbate, Sergio; Lebon, France; Castellucci, Nicola; Sabatino, Piera; Tomasini, Claudia

    2012-07-20

    Employing VCD spectroscopy, we demonstrate that the structural behavior of the oligomers Boc-(L-Phe-L-Oxd)(n)-OBn is similar from n = 2 to n = 6; ab initio calculations for the n = 1 case provide physical insight into the conformational properties. Further information is gained by IR, (1)H NMR, and ECD spectroscopies. ECD spectra suggest the presence of different conformations between n = 1 on one side and longer chain foldamers on the other side. VCD and absorption IR spectra in methanol solutions can be interpreted as indicative of a PPII structure. In the case of Boc-L-Phe-L-Oxd-OBn, VCD spectra in CCl(4) and detailed DFT computational analysis allow one to demonstrate that the most populated conformers exhibit backbone dihedral angles similar to those of a PPII geometry. This is a remarkable outcome, as we had previously demonstrated that the Boc-(L-Ala-D-Oxd)(n)-OBn series folds in a β-band ribbon spiral that is a subtype of the 3(10) helix.

  14. Analysis of human blood plasma and hen egg white by chiroptical spectroscopic methods (ECD, VCD, ROA).

    PubMed

    Synytsya, Alla; Judexová, Miluše; Hrubý, Tomáš; Tatarkovič, Michal; Miškovičová, Michaela; Petruželka, Luboš; Setnička, Vladimír

    2013-06-01

    Chiroptical methods are widely used in structural and conformational analyses of biopolymers. The application of these methods to investigations of biofluids would provide new avenues for the molecular diagnosis of protein-misfolding diseases. In this work, samples of human blood plasma and hen egg white were analyzed using a combination of conventional and chiroptical methods: ultraviolet absorption/electronic circular dichroism (UV/ECD), Fourier transform infrared absorption/vibrational circular dichroism (FTIR/VCD), and Raman scattering/Raman optical activity (Raman/ROA). For comparison, the main components of these substances--human serum albumin (HSA) and ovalbumin (Ova)--were also analyzed by these methods. The ultraviolet region of the ECD spectrum was analyzed using the CDNN CD software package to evaluate the secondary structures of the proteins. The UV/ECD, FTIR/VCD, and Raman/ROA spectra of the substances were quite similar to those of the corresponding major proteins, while some differences were also detected and explained. The conclusions drawn from the FTIR/VCD and Raman/ROA data were in good agreement with the secondary structures calculated from ECD. The results obtained in this work demonstrate that the chiroptical methods used here can be applied to analyze not only pure protein solutions but also more complex systems, such as biological fluids.

  15. VCD spectroscopy as a novel probe for chirality transfer in molecular interactions.

    PubMed

    Sadlej, Joanna; Dobrowolski, Jan Cz; Rode, Joanna E

    2010-05-01

    Most of the research in contemporary physical chemistry is devoted to the development of methods that extend our understanding, interpretation, and capacity to predict structural properties and dynamic behavior of molecules. The optical and magnetic spectroscopies, as well as diffraction techniques, are the principal methods for studying properties of molecules, biomolecules, and biopolymers of which the vast majority are chiral. On the other hand, information on molecular configuration can be obtained mainly from optical spectroscopies because other well-established spectroscopic techniques used for structural investigations, such as crystallographic, ESR, and NMR methods, do not allow for registration of signals from an individual conformer owing to intrinsic slow response to structural changes. This is the reason why the optical spectroscopy methods, based on natural chiroptical phenomena, have become so important and their renaissance in the last decade is noticed. Vibrational circular dichroism (VCD) spectroscopy is one such chiroptical technique that sheds new light on many important phenomena studied intensively. We provide an overview of recent theoretical predictions and innovative VCD observations of chirality transfer (called by other authors "induced chirality") from a chiral molecule to an achiral one as a result of hydrogen bond interactions between them. In this tutorial review we search for answers as to whether we can obtain further information about intermolecular interactions using the VCD technique. In our opinion this technique has opened new horizons for both understanding and monitoring intermolecular interactions and it could be used as a relatively new and powerful physicochemical method.

  16. Structure and absolute configuration of ginkgolide B characterized by IR- and VCD spectroscopy.

    PubMed

    Andersen, Niels H; Christensen, Niels Johan; Lassen, Peter R; Freedman, Teresa B N; Nafie, Laurence A; Strømgaard, Kristian; Hemmingsen, Lars

    2010-02-01

    Experimental and calculated (B3LYP/6-31G(d)) vibrational circular dichroism (VCD) and IR spectra are compared, illustrating that the structure and absolute configuration of ginkgolide B (GB) may be characterized directly in solution. A conformational search for GB using MacroModel and subsequent DFT optimizations (B3LYP/6-31G(d)) provides a structure for the lowest energy conformer which agrees well with the structure determined by X-ray diffraction. In addition, a conformer at an energy of 7 kJ mol(-1) (B3LYP/6-311+G(2d,2p)) with respect to the lowest energy conformer is predicted, displaying different intramolecular hydrogen bonding. Differences between measured and calculated IR and VCD spectra for GB at certain wavenumbers are rationalized in terms of interactions with solvent, intermolecular GB-GB interactions, and the potential presence of more than one conformer. This is the first detailed investigation of the spectroscopic fingerprint region (850-1300 cm(-1)) of the natural product GB employing infrared absorption and VCD spectroscopy.

  17. Optical coherence tomography imaging and fluorescence spectroscopy of a novel rat model of ovarian cancer

    NASA Astrophysics Data System (ADS)

    Kanter, Elizabeth; Walker, Ross; Marion, Sam; Hoyer, Patricia; Barton, Jennifer K.

    2005-08-01

    Ovarian cancer is relatively rare but is the fifth leading cause of death from cancer in women. Little is known about the precursors and early stages of ovarian cancer partially due to the lack of a realistic animal model. A cohesive model that incorporates ovarian cancer induction into a menopausal rodent would be well suited for comprehensive studies of ovarian cancer, and non-destructive imaging would allow carcinogenesis to be followed. Optical Coherence Tomography (OCT) and Light-Induced Fluorescence (LIF) are minimally invasive optical modalities that allow both structural and biochemical changes to be noted. Rat ovaries were exposed to 4-vinylcyclohexene diepoxide (VCD) for 20 days in order to destroy the primordial follicles. Sutures coated with 7,12-dimethylbenz(a)anthracene (DMBA) were implanted in the right ovary, in order to produce epithelial based ovarian cancers. Rats were sacrificed at 1, 3, and 5 months and ovaries were harvested and imaged with a combined OCT/LIF system. Histology was preformed on the harvested ovaries and any pathology determined. OCT was able to visualize follicle loss and DMBA-induced abnormalities. LIF spectra were also different between cycling, follicle deplete, and DMBA-exposed ovaries. Overall this pilot study demonstrated the feasibility of both the animal model and optical imaging.

  18. 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

  19. Determination of a low-level percent enantiomer of a compound with no ultraviolet chromophore using vibrational circular dichroism (VCD): enantiomeric purity by VCD of a compound with three chiral centers.

    PubMed

    Kott, Laila; Petrovic, Jelena; Phelps, Dean; Roginski, Robert; Schubert, Jared

    2014-01-01

    The chiral configuration of three of the four chiral centers in the investigational drug MLN4924 is locked by an intermediate (1S,2S,4R)-4-amino-2-(hydroxymethyl)cyclopentanol (designated as INT1a). The intermediate INT1a is a key component to the molecule, but its multiple chiral centers and lack of chromophore make it challenging to analyze for chiral purity of the desired enantiomer when it is contaminated with a small amount of its undesired enantiomer. Vibrational circular dichroism (VCD) is a technique that uses the infrared (IR) regions of the electromagnetic spectrum and as INT1a contains IR active groups, we considered using VCD to determine the chiral purity of INT1a. Since the VCD spectra of enantiomers are of equal intensity and opposite in sign, it was possible to construct calibration curves to detect the presence of low levels of this compound in the presence of its enantiomer. By normalizing the observed intensities of the VCD signals with the observed IR spectra, a partial least squares model was constructed having a root mean squared error of cross validation of 0.46% absolute over a range of 97 to 99.9% pure enantiomer (or 97-99.8% enantiomeric excess). This work demonstrates that VCD can be used for the low-level detection of a compound in the presence of its enantiomer and thus eliminates the need for an ultraviolet chromophore and chromatographic separation of the two enantiomers.

  20. 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.

  1. 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.

  2. Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid.

    PubMed

    Góbi, Sándor; Vass, Elemér; Magyarfalvi, Gábor; Tarczay, György

    2011-08-21

    The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (∼0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).

  3. Vibrational circular dichroism (VCD) studies on disaccharides in the CH region: toward discrimination of the glycosidic linkage position.

    PubMed

    Taniguchi, Tohru; Monde, Kenji

    2007-04-07

    The structural features of carbohydrates are a combination of 1) sequence and types of mono-sugars, 2) stereochemistry of their glycosidic linkages, and 3) their glycosidic linkage sites. We performed the first systematic VCD study on glycoside linking site discrimination. VCD spectra, in the CH stretching region from 2000 to 4000 cm(-1), of eleven glucobioses (trehalose (alpha1-alpha1), neotrehalose (alpha1-beta1), isotrehalose (beta1-beta1), kojibiose (alpha1-2), nigerose (alpha1-3), maltose (alpha1-4), isomaltose (alpha1-6), sophorose (beta1-2), laminaribiose (beta1-3), cellobiose (beta1-4), gentiobiose (beta1-6)) suggested a possible new discrimination method for glyco analysis, while VCD spectra in the mid-IR region distinguished the stereochemistry (alpha or beta) of the glycosidic linkage. Both reducing and nonreducing glucobioses showed different VCD spectral features compared to their constituent D-glucose and the anomer-fixed model compounds. Interresidue interaction such as hydrogen bonding was suggested to cause these spectral differences. Interplay between residues is a common phenomenon and thus VCD analysis could be applicable to other di-, oligo- or poly-saccharides. Several isotropic labeled compounds were also measured to support spectral assignment and interpretation.

  4. VCD spectroscopic properties of the beta-hairpin forming miniprotein CLN025 in various solvents.

    PubMed

    Hatfield, Marcus P D; Murphy, Richard F; Lovas, Sándor

    2010-05-01

    Electronic and vibrational circular dichroism are often used to determine the secondary structure of proteins, because each secondary structure has a unique spectrum. Little is known about the vibrational circular dichroic spectroscopic features of the beta-hairpin. In this study, the VCD spectral features of a decapeptide, YYDPETGTWY (CLN025), which forms a stable beta-hairpin that is stabilized by intramolecular weakly polar interactions and hydrogen bonds were determined. Molecular dynamics simulations and ECD spectropolarimetry were used to confirm that CLN025 adopts a beta-hairpin in water, TFE, MeOH, and DMSO and to examine differences in the secondary structure, hydrogen bonds, and weakly polar interactions. CLN025 was synthesized by microwave-assisted solid phase peptide synthesis with N(alpha)-Fmoc protected amino acids. The VCD spectra displayed a (-,+,-) pattern with bands at 1640 to 1656 cm(-1), 1667 to 1687 cm(-1), and 1679 to 1686 cm(-1) formed by the overlap of a lower frequency negative couplet and a higher frequency positive couplet. A maximum IR absorbance was observed at 1647 to 1663 cm(-1) with component bands at 1630 cm(-1), 1646 cm(-1), 1658 cm(-1), and 1675 to 1680 cm(-1) that are indicative of the beta-sheet, random meander, either random meander or loop and turn, respectively. These results are similar to the results of others, who examined the VCD spectra of beta-hairpins formed by (D)Pro-Xxx turns and indicated that observed pattern is typical of beta-hairpins.

  5. Photoisomerization of a Chiral Imine Molecular Switch Followed by Matrix-Isolation VCD Spectroscopy.

    PubMed

    Pollok, Corina H; Riesebeck, Tim; Merten, Christian

    2017-02-06

    Characterizing the stereochemistry of transient photoisomerization products remains a big challenge for the design of molecular machines, such as unidirectional molecular motors. Often these states are not stable long enough to be characterized in detail using conventional spectroscopic tools. The structurally simple camphorquinone imine 1 serves to illustrate the advantage of combining the matrix-isolation technique with vibrational circular dichroism (VCD) spectroscopy for the investigation of photoisomerizations of chiral molecules. In particular, it is shown that both (E)- and (Z)-1 can be generated photochemically at cryogenic temperatures in an argon matrix, and more importantly, that the stereochemistry of both switching states can be characterized reliably.

  6. Solvent effects on IR and VCD spectra of helical peptides: DFT-based static spectral simulations with explicit water.

    PubMed

    Kubelka, Jan; Huang, Rong; Keiderling, Timothy A

    2005-04-28

    Simulations of IR and VCD spectra are carried out for model alpha-helical, 3(10)-helical, and 3(1)-helical (polyProII-like) oligopeptides, with up to 21 amide groups, and including explicit consideration of effects of directly hydrogen-bonded solvent (water). Parameters used were obtained from ab initio density functional theory (DFT) computations of force field, atomic polar and axial tensors for oligopeptides of 5 to 7 amides, whose structures were constrained in (phi,psi) to target the secondary structure type but otherwise fully optimized. By comparison with experimental data as well as with calculations for identical but isolated (gas phase) peptides, the computed effects of an inner shell of aqueous solvent on the vibrational spectra of helical oligopeptides are illustrated. The interaction with solvent causes significant frequency shifts of the amide bands, but only minor changes in the characteristic IR intensity distributions and splittings and the VCD band shapes. Better agreement with experimental band shapes is achieved for the alpha-helical amide I' (N-deuterated) VCD by inclusion of explicit solvent in the calculations. Some improvements are also observed in theoretical VCD predictions for 13C labeled alpha-helical peptides when solvated models are used. However, the qualitative isotopic splitting patterns are preserved and just shifted in frequency due to consistent, solvent independent interamide coupling constants. The critical match of experiment and theory for relative positions of transitions in peptides with specifically separated 13C=O labels, including and neglecting solvent, confirms the stability of the coupling interactions. Despite these solvation effects, the calculated VCD band shape of the amide I mode is shown to be a reliable conformational probe, since it remains basically insensitive to frequency shifts caused by environment. Thus theoretical VCD simulations, even vacuum calculations, are shown to provide useful spectral

  7. VCD studies on cyclic peptides assembled from L-α-amino acids and a trans-2-aminocyclopentane- or trans-2-aminocyclohexane carboxylic acid.

    PubMed

    Vass, E; Strijowski, U; Wollschläger, K; Mándity, I M; Szilvágyi, G; Jewgiński, M; Gaus, K; Royo, S; Majer, Z; Sewald, N; Hollósi, M

    2010-11-01

    The increasing interest in peptidomimetics of biological relevance prompted us to synthesize a series of cyclic peptides comprising trans-2-aminocyclohexane carboxylic acid (Achc) or trans-2-aminocyclopentane carboxylic acid (Acpc). NMR experiments in combination with MD calculations were performed to investigate the three-dimensional structure of the cyclic peptides. These data were compared to the conformational information obtained by electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectroscopy. Experimental VCD spectra were compared to theoretical VCD spectra computed quantum chemically at B3LYP/6-31G(d) density functional theory (DFT) level. The good agreement between the structural features derived from the VCD spectra and the NMR-based structures underlines the applicability of VCD in studying the conformation of small cyclic peptides.

  8. Chiroptical Properties of Cryptophane-223 and -233 Investigated by ECD, VCD, and ROA Spectroscopy.

    PubMed

    Brotin, Thierry; Daugey, Nicolas; Vanthuyne, Nicolas; Jeanneau, Erwann; Ducasse, Laurent; Buffeteau, Thierry

    2015-07-09

    Enantiopure cryptophane derivatives 1 and 2, possessing linkers of different nature (ethylenedioxy and propylenedioxy) connecting the two cyclotribenzylenes (CTB) units, were separated by HPLC using chiral stationary phases. X-ray crystallographic structures of the four enantiomers (+)-1, (-)-1, (+)-2, and (-)-2 have been obtained, allowing the unambiguous determination of their absolute configuration (AC) in the solid state. The chiroptical properties of compounds 1 and 2 were determined from polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) experiments and were compared to those of cryptophane-A (3) derivative. VCD, ROA and ECD spectra of 1 and 2 were calculated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, respectively, to confirm the AC of the cryptophane derivatives in solution. The (+)-PP and (-)-MM configurations were established for compounds 1 and 2 in chloroform solution, as already reported for the two enantiomers of 3. This result is in agreement with the X-ray structures of the two enantiomers of 1 and 2.

  9. Understanding the origin of the VCD signals on the basis of a nonredundant coordinate definition.

    PubMed

    Nieto-Ortega, Belén; Casado, Juan; López Navarrete, Juan T; Ramírez, Francisco J; Tommasini, Matteo; Longhi, Giovanna; Mazzeo, Giuseppe; Abbate, Sergio

    2015-06-09

    The relationships between the chiroptical activity and the vibrational normal modes of epichlorohydrin have been investigated on the basis of a nonredundant internal coordinate definition not reported until now. These coordinates were verified by comparing, for the lower energy conformers, the diagonal quadratic force constants and were found to display similar values among conformers and to be consistent with the molecular structure of epichlorohydrin and its vibrational circular dichroism (VCD) spectrum. Boltzmann population factors were used to calculate the weighted sum of the individual VCD and IR spectra of the three lower energy conformers, which accurately fitted the experimental spectra of (R)-epichlorohydrin. The electric and magnetic transition dipole moments of the 24 vibrational normal modes were calculated for the most stable conformers. The combined analysis of these vectors and the normal mode description, given in terms of the potential energy distribution, allowed us to investigate the role of the functional groups (methylene, chlorine) and the type of internal coordinates (stretching, bending, etc.) in the chiroptical activity of the vibrations.

  10. Rictor/mTORC2 Pathway in Oocytes Regulates Folliculogenesis, and Its Inactivation Causes Premature Ovarian Failure*

    PubMed Central

    Chen, Zhenguo; Kang, Xiangjin; Wang, Liping; Dong, Heling; Wang, Caixia; Xiong, Zhi; Zhao, Wanlu; Jia, Chunhong; Lin, Jun; Zhang, Wen; Yuan, Weiping; Zhong, Mei; Du, Hongzi; Bai, Xiaochun

    2015-01-01

    Molecular basis of ovarian folliculogenesis and etiopathogenesis of premature ovarian failure (POF), a common cause of infertility in women, are not fully understood. Mechanistic target of rapamycin complex 2 (mTORC2) is emerging as a central regulator of cell metabolism, proliferation, and survival. However, its role in folliculogenesis and POF has not been reported. Here, we showed that the signaling activity of mTORC2 is inhibited in a 4-vinylcyclohexene diepoxide (VCD)-induced POF mouse model. Notably, mice with oocyte-specific ablation of Rictor, a key component of mTORC2, demonstrated POF phenotypes, including massive follicular death, excessive loss of functional ovarian follicles, abnormal gonadal hormone secretion, and consequently, secondary subfertility in conditional knock-out (cKO) mice. Furthermore, reduced levels of Ser-473-phosphorylated Akt and Ser-253-phosphorylated Foxo3a and elevated pro-apoptotic proteins, Bad, Bax, and cleaved poly ADP-ribose polymerase (PARP), were observed in cKO mice, replicating the signaling alterations in 4-VCD-treated ovaries. These results indicate a critical role of the Rictor/mTORC2/Akt/Foxo3a pro-survival signaling axis in folliculogenesis. Interestingly, loss of maternal Rictor did not cause obvious developmental defects in embryos or placentas from cKO mice, suggesting that maternal Rictor is dispensable for preimplantation embryonic development. Our results collectively indicate key roles of Rictor/mTORC2 in folliculogenesis, follicle survival, and female fertility and support the utility of oocyte-specific Rictor knock-out mice as a novel model for POF. PMID:25564616

  11. 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.

  12. Absolute configurations of fungal and plant metabolites by chiroptical methods. ORD, ECD, and VCD studies on phyllostin, scytolide, and oxysporone.

    PubMed

    Mazzeo, Giuseppe; Santoro, Ernesto; Andolfi, Anna; Cimmino, Alessio; Troselj, Pavle; Petrovic, Ana G; Superchi, Stefano; Evidente, Antonio; Berova, Nina

    2013-04-26

    The absolute configuration (AC) of the bioactive metabolites phyllostin (1) and scytolide (2), two hexahydro-1,4-benzodioxines produced by Phyllosticta cirsii, and oxysporone (3), a dihydrofuropyranone recently isolated from a strain of Diplodia africana, has been assigned by computational analysis of their optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectra. Computational prediction of ORD, ECD, and VCD allowed us to assign (3S,4aR,8S,8aR) AC to naturally occurring (-)-1, while (4aR,8S,8aR) AC was assigned to (-)-2 employing only ECD and VCD, because in this case ORD analysis turned out to be unsuitable for AC assignment. Theoretical prediction of both ORD and ECD spectra of 3 led to assignment of (4S,5R,6R) AC to (+)-3. In this case a satisfactory agreement between experimental and calculated VCD spectra was obtained only after taking into account solvent effects. This study shows that in the case of flexible and complex natural products only a concerted application of more than a single chiroptical technique permits unambiguous assignment of absolute configuration.

  13. VCD spectroscopic investigation of enantiopure cyclic beta-lactams obtained through Lipolase-catalyzed enantioselective ring-opening reaction.

    PubMed

    Vass, Elemér; Hollósi, Miklós; Forró, Eniko; Fülöp, Ferenc

    2006-09-01

    A direct enzymatic method for the preparation of cyclic beta-lactams and beta-amino acids was recently developed, involving the Lipolase-catalyzed enantioselective hydrolysis of racemic beta-lactams in an organic solvent. Vibrational circular dichroism (VCD) spectroscopy combined with quantum chemical calculations at ab initio (DFT) level of theory has now been applied to determine the absolute configuration and conformation of a series of cyclic beta-lactams (1-10). The absolute configuration of 8 was derived from X-ray crystallography. Only indirect evidence was available for 1, 2, 5, 6, and 7. The absolute configuration of the new lactams 3, 4, 9, and 10 was not known previously. The VCD analysis indicated the homochirality of the studied lactams. The conformation of the flexible beta-lactams was also predicted from the VCD data. Even in the cases where multiple conformers are allowed, the predominance of one conformer was found, with the exception of 2, being present as a mixture of four conformers. Beta-lactams tend to form H-bonded dimers. The fine structure of the amide I VCD band suggested that only a small population of H-bonded dimers is formed in deuterated chloroform.

  14. VTD is superior to VCD prior to intensive therapy in multiple myeloma: results of the prospective IFM2013-04 trial.

    PubMed

    Moreau, Philippe; Hulin, Cyrille; Macro, Margaret; Caillot, Denis; Chaleteix, Carine; Roussel, Murielle; Garderet, Laurent; Royer, Bruno; Brechignac, Sabine; Tiab, Mourad; Puyade, Mathieu; Escoffre, Martine; Stoppa, Anne-Marie; Facon, Thierry; Pegourie, Brigitte; Chaoui, Driss; Jaccard, Arnaud; Slama, Borhane; Marit, Gerald; Laribi, Karim; Godmer, Pascal; Luycx, Odile; Eisenmann, Jean-Claude; Allangba, Olivier; Dib, Mamoun; Araujo, Carla; Fontan, Jean; Belhadj, Karim; Wetterwald, Marc; Dorvaux, Véronique; Fermand, Jean-Paul; Rodon, Philippe; Kolb, Brigitte; Glaisner, Sylvie; Malfuson, Jean-Valere; Lenain, Pascal; Biron, Laetitia; Planche, Lucie; Caillon, Helene; Avet-Loiseau, Herve; Dejoie, Thomas; Attal, Michel

    2016-05-26

    The Intergroupe Francophone du Myélome conducted a randomized trial to compare bortezomib-thalidomide-dexamethasone (VTD) with bortezomib-cyclophosphamide-dexamethasone (VCD) as induction before high-dose therapy and autologous stem cell transplantation (ASCT) in patients with newly diagnosed multiple myeloma. Overall, a total of 340 patients were centrally randomly assigned to receive VTD or VCD. After 4 cycles, on an intent-to-treat basis, 66.3% of the patients in the VTD arm achieved at least a very good partial response (primary end point) vs 56.2% in the VCD arm (P = .05). In addition, the overall response rate was significantly higher in the VTD arm (92.3% vs 83.4% in the VCD arm; P = .01). Hematologic toxicity was higher in the VCD arm, with significantly increased rates of grade 3 and 4 anemia, thrombocytopenia, and neutropenia. On the other hand, the rate of peripheral neuropathy (PN) was significantly higher in the VTD arm. With the exception of hematologic adverse events and PN, other grade 3 or 4 toxicities were rare, with no significant differences between the VTD and VCD arms. Our data support the preferential use of VTD rather than VCD in preparation for ASCT. This trial was registered at www.clinicaltrials.gov as #NCT01564537 and at EudraCT as #2013-003174-27.

  15. A rapid alternative to X-ray crystallography for chiral determination: case studies of vibrational circular dichroism (VCD) to advance drug discovery projects.

    PubMed

    Wesolowski, Steven S; Pivonka, Don E

    2013-07-15

    The absolute stereochemistry of chiral drugs is usually established via X-ray crystallography. However, vibrational circular dichroism (VCD) spectroscopy coupled with quantum mechanics simulations offers a rapid alternative to crystallography and is readily applied to both crystalline and non-crystalline samples. VCD is an effective complement to X-ray analysis of drug candidates, and it can be used as a high-throughput means of assessing absolute stereochemistry at all phases of the discovery process (hundreds of assignments per year). The practical implementation (or fee-for-service outsourcing) of VCD and selected case studies are illustrated with an emphasis on providing utility and impact to pharmaceutical discovery programs.

  16. Reassignment of the OSe-VCd complex in CdSe

    NASA Astrophysics Data System (ADS)

    Bastin, Dirk; Lavrov, E. V.; Weber, J.

    2014-02-01

    An IR absorption study of CdSe single crystals is presented. The as-received material revealed three absorption lines at 1094.2, 1107.5, and 1126.3 cm-1, which were previously assigned to the OSe-VCd complex [G. Chen et al., Phys. Rev. Lett. 101, 195502 (2008)] We show that each of the lines is accompanied by a number of weaker satellites with intensities which match the natural abundances of sulfur isotopes. In contrast to the original identification it is suggested that these peaks are local vibrational modes of a SOn complex. The three modes correspond to different orientations of the complex in the CdSe lattice. Arguments are presented in favor of 2 oxygen atoms (n = 2) in the complex. Measurements with uniaxial stress applied to the samples revealed defect symmetries and activation energies for the defect reorientation. The complex was found to be stable up to 750 °C.

  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. 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.

  19. A comparative VCD study of methyl mandelate in methanol, dimethyl sulfoxide, and chloroform: explicit and implicit solvation models.

    PubMed

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

    2013-02-07

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of methyl mandelate, a prototype chiral molecule, in a series of organic solvents, namely methanol (MeOH-d(4)), dimethyl sulfoxide (DMSO-d(6)), and chloroform (CDCl(3)), have been measured in the finger print region from 1800 to 1150 cm(-1). Implicit solvation models in the form of polarizable continuum model and explicit solvation models have been employed independently and simultaneously. The goal is to evaluate their efficiencies in dealing with solvent effects in each solution and to establish a general strategy to adequately account for effects of solvents. Molecular dynamics (MD) simulation and radial distribution function analysis have been performed to aid the construction of the explicit solvation models. Initial geometry searches have been carried out at the B3LYP/6-31G(d) level for the methyl mandelate monomer and its explicit 1 : 1 and 1 : 2 solute-solvent hydrogen-bonded complexes. B3LYP/cc-pVTZ has been used for all the final geometry optimizations, the vibrational frequency, VA and VCD intensity, and optical rotation dispersion (ORD) calculations. The results show that inclusion of solvent explicitly and implicitly at the same time has significant impacts on the appearance of the VA and VCD spectra, and is crucial for reliable spectral assignments when solvents are capable of hydrogen-bonding interactions with solutes. When no strong solvent-solute hydrogen-bonding interactions in the case of chloroform are expected, the gas phase monomer model is adequate for spectral interpretation, while inclusion of implicit solvation improves the frequency agreement with experiment. ORD spectra of methyl mandelate in the aforementioned solvents at different concentrations under 5 excitation wavelengths have also been measured. The comparison between the calculated and the experimental ORD spectra supports the conclusions drawn from the VA and VCD investigations.

  20. Avian pancreatic polypeptide fragments refold to native aPP conformation when combined in solution: a CD and VCD study.

    PubMed

    Copps, Jeffrey; Murphy, Richard F; Lovas, Sándor

    2006-09-01

    An equimolar mixture of avian pancreatic polypeptide (aPP) fragments aPP(1-11)-NH2 and Ac-aPP(12-36) had an electronic circular dichroism (ECD) spectrum that was similar to that of whole aPP in H2O and even more so in 30% (v/v) trifluoroethanol (TFE) in 15 mM Na2HPO4, but was different from the sum of the spectra of the individual fragments. The vibrational circular dichroism (VCD) spectrum of the combined fragments in 30% (v/v) TFE in 15 mM Na2HPO4 in D2O was also similar to that of the intact aPP and unlike the sum of the VCD spectra of the fragments. The interaction of these fragments is thus sufficient to support the conformation of whole aPP. This study demonstrates that VCD, in combination with ECD, is useful for the study of protein-protein interactions.

  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. Harmonic and anharmonic features of IR and NIR absorption and VCD spectra of chiral 4-X-[2.2]paracyclophanes.

    PubMed

    Abbate, Sergio; Castiglioni, Ettore; Gangemi, Fabrizio; Gangemi, Roberto; Longhi, Giovanna; Ruzziconi, Renzo; Spizzichino, Sara

    2007-08-02

    The vibrational absorption spectra and vibrational circular dichroism (VCD) spectra of both enantiomers of 4-X-[2.2]paracyclophanes (X = COOCD3, Cl, I) have been recorded for a few regions in the range of 900-12000 cm(-1). The analysis of the VCD spectra for the two IR regions, 900-1600 cm(-1) and 2800-3200 cm(-1), is conducted by comparing with DFT calculations of the corresponding spectra; the latter region reveals common motifs of vibrational modes for the three molecules for aliphatic CH stretching fundamentals, whereas in the mid-IR region, one is able to identify specific signatures arising from the substituent groups X. In the CH stretching region between 2900 and 2800 cm(-1), we identify and interpret a group of three IR VCD bands due to HCH bending overtone transitions in Fermi resonance with CH stretching fundamental transitions. The analysis of the NIR region between approximately 8000 and approximately 9000 cm(-1) for X = COOCD3 reveals important features of the aromatic CH stretching overtones that are of value since the aromatic CH stretching fundamentals are almost silent. The intensifying of such overtones is attributed to electrical anharmonicity terms, which are evaluated here by ab initio methods and compared with literature data.

  3. Identification of the specific, shutter-like conformational reorientation in a chiroptical switching polycarbodiimide by VCD spectroscopy.

    PubMed

    Merten, Christian; Reuther, James F; DeSousa, Joseph D; Novak, Bruce M

    2014-06-21

    The specific conformational states responsible for the unique, reversible temperature- and solvent-driven chiroptical switching process experienced by poly(N-1-naphthyl-N'-octadecyl-carbodiimide) (PNOC) have been identified using VCD spectroscopy and DFT calculations. The distinct VCD spectra of PNOC corresponding to the two specific conformations were obtained for the polymer dissolved in DCM-d2 (state A) and CDCl3 (predominantly state B). To specifically assign the structures of both conformations, two simplified 7mer models were constructed and optimized using DFT calculations. The theoretical spectra associated with these model conformations show a high level of agreement when compared to the experimental VCD spectra. The two states consist of the naphthyl pendant groups aligned directionally opposing the helical rotation (model A) and aligned with the helicity of the backbone (model B). This pendant reorientation causes very large OR and ECD Cotton effect inversions upon modification to the temperature or solvent composition of dilute (+)-PNOC solutions in specific solvents. In addition, the pendant group equilibrium from state A to B causes a contraction of the helical pitch from the more expanded 5/1 pitch to the more contracted 7/2 pitch resulting in increased disorder of the solvation sphere surrounding the polymer chain.

  4. 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.

  5. Study of the photoinduced supramolecular chirality in columnar liquid crystals by infrared and VCD spectroscopies.

    PubMed

    Avilés Moreno, Juan Ramón; López González, Juan Jesús; Partal Ureña, Francisco; Vera, Francisco; Ros, M Blanca; Sierra, Teresa

    2012-04-26

    IR and VCD spectroscopies are employed to clarify the molecular origins of supramolecular chirality in azobenzene-containing columnar liquid crystals. The different columnar mesomorphic assemblies, Colr and Colh, of an achiral and a chiral propeller-like hydrogen-bonded complex, respectively, are used for this study. The mesomorphic behavior of the achiral complex is studied here for the first time, and the structural parameters of its Colr mesophase are determined by X-ray diffraction. Both complexes bear azobenzene units and this makes it possible to implement photoresponsive columnar architectures, the chirality of which can be induced and modulated by irradiation with 488 nm circularly polarized light (CPL). Thin films of the respective rectangular and hexagonal columnar phases of these complexes have been processed in order to study the IR absorption spectra and the vibrational circular dichroism responses upon irradiation with CPL. These studies allow confirming that the outer part of the columns, consisting on azobenzene groups, is mainly involved in the photoinduced supramolecular chirality, rather than the inner part of the columns where a melamine core is located. This supports a structural model based on the helical disposition of the azobenzene groups along the stacked propeller-like complexes.

  6. 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.

  7. Absolute Configuration and Conformation of Two Fráter-Seebach Alkylation Reaction Products by Film VCD and ECD Spectroscopic Analyses.

    PubMed

    Poopari, Mohammad Reza; Dezhahang, Zahra; Shen, Ke; Wang, Lei; Lowary, Todd L; Xu, Yunjie

    2015-01-02

    Two chiroptical spectroscopic techniques, namely, electronic and vibrational circular dichroism (ECD and VCD), as well as NMR spectroscopy have been utilized to determine the absolute configurations and geometries of two Fráter-Seebach alkylation reaction products with long hydrocarbon chains. The experimental studies have been complemented with density functional theory calculations. Strong characteristic bisignate VCD signatures in the carbonyl stretching region have been observed for both compounds in film state. Truncated models, i.e., without the long CH2 chains, have been utilized to examine different hydrogen-bonding topologies between two monomeric moieties and to simulate the corresponding IR and VCD spectra of the dimers. In addition, the exciton coupling model has also been applied to the -C═O groups of the two monomeric moieties, which can be coupled through intermolecular hydrogen-bonding. On the basis of these simplified approaches, the absolute configurations of the compounds have been unambiguously assigned using VCD and ECD spectroscopy. Spectral simulations in the IR and UV-vis regions have also been carried out with the full dimers to validate the fitness of the truncated model. The study shows that the combination of the film VCD and ECD techniques is a relatively straightforward method to determine the absolution configurations of such synthetic compounds.

  8. Chiral recognition of amino acid enantiomers by a crown ether: chiroptical IR-VCD response and computational study.

    PubMed

    Avilés-Moreno, Juan Ramón; Quesada-Moreno, María Mar; López-González, Juan Jesús; Martínez-Haya, Bruno

    2013-08-15

    We report on a combined experimental and computational study of the chiral recognition of the amino acid serine in protonated form (L/D-SerH(+)), by the crown ether (all-S)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (S-18c6H4). Infrared and vibrational circular dichroism spectroscopies (IR-VCD) are employed to characterize the chiroptical response of the complexes formed by S-18c6H4 with the L-SerH(+) and D-SerH(+) enantiomers in dried thin films obtained from aqueous solutions. The study focuses on vibrational modes directly related to the intermolecular hydrogen bonds between the crown ether derivative and serine, responsible for crown-serine binding, namely, the C═O and C-O stretching modes, and on the C-O-H bending mode, which yield intense IR and VCD signals in the range of wavenumbers 900-2000 cm(-1). The experimental spectra are analyzed in combination with a computational structural survey and optimization at different levels of density functional theory. The conformational landscape of the complexes is found to be primarily governed by a bowl-like structure of the crown ether host and a tripodal coordination of the protonated R-NH3(+) group of serine with the oxygen atoms of the central ether ring. Additionally, one or two of the carboxylic side groups of the crown ether interact with the -COH and -COOH groups of serine. Chiral selectivity is probed by recording the IR and VCD spectra of dried thin films obtained from aqueous solutions with equimolar concentrations of the two serine enantiomers and the macrocycle. The results demonstrate a marked chiral recognition of L-SerH(+) relative to D-SerH(+) by the S-18c6H4 substrate, which arises from the favorable host-guest coordination through H-bonds at optimum distances and collinear orientations, also involving a limited distortion of the crown ether backbone.

  9. Isolation of the major chiral compounds from Bubonium graveolens essential oil by HPLC and absolute configuration determination by VCD.

    PubMed

    Said, Mohammed El-Amin; Bombarda, Isabelle; Naubron, Jean-Valère; Vanloot, Pierre; Jean, Marion; Cheriti, Abdelkrim; Dupuy, Nathalie; Roussel, Christian

    2017-02-01

    The chirality issues in the essential oils (EOs) of leaves and flowers from Bubonium graveolens were addressed by chiral high-performance liquid chromatography (HPLC) with polarimetric detection and vibrational circular dichroism (VCD). The chemical compositions of the crude oils of three samples were established by gas chromatography / mass spectrometry (GC/MS). The well-known cis-chrysanthenyl acetate (1), oxocyclonerolidol (2), and the recently disclosed cis-acetyloxychrysanthenyl acetate (3), the three major chiral compounds, were isolated by preparative HPLC. The naturally occurring oxocycloneroledol (2), mostly found in the leaf oil (49.4-55.6%), presents a (+) sign in the mobile phase during HPLC on a chiral stationary phase (CSP) with a Jasco polarimetric detection. The naturally occurring cis-chrysanthenyl acetate (1) and cis-acetyloxychrysanthenyl acetate (3), mostly found in the flower EO (35.9-74.9% and 10.0-34.3%, respectively), both present a (-) sign. HPLC on a CSP with polarimetric detection is an unprecedented approach to readily differentiate the flower and leaf EOs according to their chiral signature. The comparison of the experimental and calculated VCD spectra of pure isolated 1, 2, and 3 provided their absolute configuration as being (1S,5R,6S)-(-)-2,7,7-trimethylbicyclo[3.1.1]hept-2-en-6-yl acetate 1, (2R,6R)-(+)-6-ethenyl-2,6-dimethyl-2-(4-methylpent-3-en-1-yl)dihydro-2H-pyran-3(4H)-one) 2 and (1S,5R,6R,7S)-(-)-7-(acetyloxy)-2,6-dimethylbicyclo[3.1.1]hept-2-en-6-yl]methyl acetate 3. Compounds 1, 2, and 3 were already known in B. graveolens but this is the first report of the absolute configuration of (+)-2 and (-)-3. The VCD chiral signatures of the crude oils were also recorded.

  10. The VCD Mouse Model of Menopause and Perimenopause for the Study of Sex Differences in Cardiovascular Disease and the Metabolic Syndrome.

    PubMed

    Brooks, H L; Pollow, D P; Hoyer, P B

    2016-07-01

    In females, menopause, the cessation of menstrual cycling, is associated with an increase in risk for several diseases such as cardiovascular disease, osteoporosis, diabetes, the metabolic syndrome, and ovarian cancer. The majority of women enter menopause via a gradual reduction of ovarian function over several years (perimenopause) and retain residual ovarian tissue. The VCD mouse model of menopause (ovarian failure in rodents) is a follicle-deplete, ovary-intact animal that more closely approximates the natural human progression through perimenopause and into the postmenopausal stage of life. In this review, we present the physiological parameters of how to use the VCD model and explore the VCD model and its application into the study of postmenopausal disease mechanisms, focusing on recent murine studies of diabetic kidney disease, the metabolic syndrome, and hypertension.

  11. Use of multiple imaging modalities to detect ovarian cancer

    NASA Astrophysics Data System (ADS)

    Kanter, Elizabeth; Walker, Ross; Marion, Sam; Hoyer, Patricia; Barton, Jennifer K.

    2005-04-01

    Ovarian cancer is not a common cancer-approximately 25,000 new cases in 2004-but it is the fifth leading cause of death from cancer in women (over 16,000 in 2004). Little is known about the precursors and early stages of ovarian cancer partially due to the lack of human samples at the early stages. A cohesive model that incorporates ovarian cancer induction into a menopausal rodent would be well suited for comprehensive studies of ovarian cancer. Non-destructive imaging would allow carcinogenesis to be followed. Optical Coherence Tomography (OCT), Optical Coherence Microscopy (OCM) and Light-Induced Fluorescence (LIF) are minimally invasive optical modalities that allow both structural and biochemical changes to be noted. Rat ovaries were exposed to 4-vinylcyclohexene diepoxide (VCD) for 20 days in order to destroy the primordial follicles. Plain sutures and sutures coated with 7,12-dimethylbenz(a)anthracene (DMBA) were implanted in the right ovary, in order to produce epithelial based ovarian cancers (a plain suture was inserted in the control). Rats were sacrificed at 4 weeks and ovaries were harvested and imaged with a combined OCT/LIF system and with the OCM. Histology was preformed on the harvested ovaries and any pathology determined. Two of the ovaries were visually abnormal; the OCT/LIF imaging confirmed these abnormalities. The normal ovary OCM and OCT images show the organized structure of the ovary, the follicles, bursa and corpus lutea are visible. The OCM images show the disorganized structure of one of the abnormal ovaries. Overall this pilot study demonstrated the feasibility of both the animal model and optical imaging.

  12. Conformational preference of a chiral terpene: vibrational circular dichroism (VCD), infrared and Raman study of S-(-)-limonene oxide.

    PubMed

    Moreno, Juan Ramón Avilés; Ureña, Francisco Partal; González, Juan Jesús López

    2009-04-14

    S-(-)-Limonene oxide (4-isopropenyl-1-methyl-7-oxabicyclo[4.1.0]heptane) is a secondary metabolite and an atmospheric pollutant product of oxidation of other terpenes, such as limonene and alpha-pinene, among others. For the first time, a theoretical study of the molecular structure and a theoretical and experimental analysis of the infrared and Raman spectra of this chemical species are presented. Theoretical calculations reveal the existence of two conformers depending on the position of the isopropenyl group (axial and equatorial) and twelve rotamers (six equatorials and six axials), with the six equatorial ones as the most stable (around 97%) on the basis of Boltzmann's distribution law. In the current work, from a reliable assignment of the IR and Raman spectra and with the help from the study of the VCD spectrum of the title compound, five rotamers have been detected experimentally in the liquid phase. The present work reveals that IR, Raman and VCD are helpful complementary techniques to characterize flexible systems, as terpenes, which present several conformers.

  13. VCD Robustness of the Amide-I and Amide-II Vibrational Modes of Small Peptide Models.

    PubMed

    Góbi, Sándor; Magyarfalvi, Gábor; Tarczay, György

    2015-09-01

    The rotational strengths and the robustness values of amide-I and amide-II vibrational modes of For(AA)n NHMe (where AA is Val, Asn, Asp, or Cys, n = 1-5 for Val and Asn; n = 1 for Asp and Cys) model peptides with α-helix and β-sheet backbone conformations were computed by density functional methods. The robustness results verify empirical rules drawn from experiments and from computed rotational strengths linking amide-I and amide-II patterns in the vibrational circular dichroism (VCD) spectra of peptides with their backbone structures. For peptides with at least three residues (n ≥ 3) these characteristic patterns from coupled amide vibrational modes have robust signatures. For shorter peptide models many vibrational modes are nonrobust, and the robust modes can be dependent on the residues or on their side chain conformations in addition to backbone conformations. These robust VCD bands, however, provide information for the detailed structural analysis of these smaller systems.

  14. 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.

  15. Cooperative use of VCD and XRD for the determination of tetrahydrobenzoisoquinolines absolute configuration: a reliable proof of memory of chirality and retention of configuration in enediyne rearrangements.

    PubMed

    Mondal, Shovan; Naubron, Jean-Valère; Campolo, Damien; Giorgi, Michel; Bertrand, Michéle P; Nechab, Malek

    2013-12-01

    The absolute configurations (AC) of azaheterocylic compounds resulting from the cascade rearrangement of enediynes involving only light atoms were unambiguously assigned by the joint use of vibrational circular dichroism (VCD) and copper radiation single crystal X-ray diffraction (XRD). These AC determinations proved that the rearrangements of enediynes proceeded with memory of chirality and retention of configuration.

  16. A Method for the Generation of Ectromelia Virus (ECTV) Recombinants: In Vivo Analysis of ECTV vCD30 Deletion Mutants

    PubMed Central

    Alejo, Ali; Saraiva, Margarida; Ruiz-Argüello, Maria Begoña; Viejo-Borbolla, Abel; de Marco, Mar Fernández; Salguero, Francisco Javier; Alcami, Antonio

    2009-01-01

    Background Ectromelia virus (ECTV) is the causative agent of mousepox, a lethal disease of mice with similarities to human smallpox. Mousepox progression involves replication at the initial site of infection, usually the skin, followed by a rapid spread to the secondary replicative organs, spleen and liver, and finally a dissemination to the skin, where the typical rash associated with this and other orthopoxviral induced diseases appears. Case fatality rate is genetically determined and reaches up to 100% in susceptible mice strains. Like other poxviruses, ECTV encodes a number of proteins with immunomodulatory potential, whose role in mousepox progression remains largely undescribed. Amongst these is a secreted homologue of the cellular tumour necrosis factor receptor superfamily member CD30 which has been proposed to modulate a Th1 immune response in vivo. Methodology/Principal Findings To evaluate the contribution of viral CD30 (vCD30) to virus pathogenesis in the infected host, we have adapted a novel transient dominant method for the selection of recombinant ECTVs. Using this method, we have generated an ECTV vCD30 deletion mutant, its corresponding revertant control virus as well as a virus encoding the extracellular domain of murine CD30. These viruses contain no exogenous marker DNA sequences in their genomes, as opposed to other ECTVs reported up to date. Conclusions/Significance We show that the vCD30 is expressed as a secreted disulfide linked trimer and that the absence of vCD30 does not impair mousepox induced fatality in vivo. Replacement of vCD30 by a secreted version of mouse CD30 caused limited attenuation of ECTV. The recombinant viruses generated may be of use in the study of the role of the cellular CD30-CD30L interaction in the development of the immune response. The method developed might be useful for the construction of ECTV mutants for the study of additional genes. PMID:19365546

  17. 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.

  18. Precision measurements of B(D+→μ+νμ), the pseudoscalar decay constant fD+, and the quark mixing matrix element |Vcd|

    NASA Astrophysics Data System (ADS)

    Ablikim, M.; Achasov, M. N.; Ai, X. C.; Albayrak, O.; Ambrose, D. J.; An, F. F.; An, Q.; Bai, J. Z.; Ferroli, R. Baldini; Ban, Y.; Bennett, J. V.; Bertani, M.; Bian, J. M.; Boger, E.; Bondarenko, O.; Boyko, I.; Braun, S.; Briere, R. A.; Cai, H.; Cai, X.; Cakir, O.; Calcaterra, A.; Cao, G. F.; Cetin, S. A.; Chang, J. F.; Chelkov, G.; Chen, G.; Chen, H. S.; Chen, J. C.; Chen, M. L.; Chen, S. J.; Chen, X.; Chen, X. R.; Chen, Y. B.; Cheng, H. P.; Chu, X. K.; Chu, Y. P.; Cronin-Hennessy, D.; Dai, H. L.; Dai, J. P.; Dedovich, D.; Deng, Z. Y.; Denig, A.; Denysenko, I.; Destefanis, M.; Ding, W. M.; Ding, Y.; Dong, C.; Dong, J.; Dong, L. Y.; Dong, M. Y.; Du, S. X.; Fan, J. Z.; Fang, J.; Fang, S. S.; Fang, Y.; Fava, L.; Feng, C. Q.; Fu, C. D.; Fu, J. L.; Fuks, O.; Gao, Q.; Gao, Y.; Geng, C.; Goetzen, K.; Gong, W. X.; Gradl, W.; Greco, M.; Gu, M. H.; Gu, Y. T.; Guan, Y. H.; Guo, A. Q.; Guo, L. B.; Guo, T.; Guo, Y. P.; Guo, Y. P.; Han, Y. L.; Harris, F. A.; He, K. L.; He, M.; He, Z. Y.; Held, T.; Heng, Y. K.; Hou, Z. L.; Hu, C.; Hu, H. M.; Hu, J. F.; Hu, T.; Huang, G. M.; Huang, G. S.; Huang, J. S.; Huang, L.; Huang, X. T.; Huang, Y.; Hussain, T.; Ji, C. S.; Ji, Q.; Ji, Q. P.; Ji, X. B.; Ji, X. L.; Jiang, L. L.; Jiang, X. S.; Jiao, J. B.; Jiao, Z.; Jin, D. P.; Jin, S.; Johansson, T.; Kalantar-Nayestanaki, N.; Kang, X. L.; Kang, X. S.; Kavatsyuk, M.; Kloss, B.; Kopf, B.; Kornicer, M.; Kuehn, W.; Kupsc, A.; Lai, W.; Lange, J. S.; Lara, M.; Larin, P.; Leyhe, M.; Li, C. H.; Li, Cheng; Li, Cui; Li, D.; Li, D. M.; Li, F.; Li, G.; Li, H. B.; Li, J. C.; Li, K.; Li, K.; Li, Lei; Li, P. R.; Li, Q. J.; Li, T.; Li, W. D.; Li, W. G.; Li, X. L.; Li, X. N.; Li, X. Q.; Li, X. R.; Li, Z. B.; Liang, H.; Liang, Y. F.; Liang, Y. T.; Lin, D. X.; Liu, B. J.; Liu, C. L.; Liu, C. X.; Liu, F. H.; Liu, Fang; Liu, Feng; Liu, H. B.; Liu, H. H.; Liu, H. M.; Liu, J.; Liu, J. P.; Liu, K.; Liu, K. Y.; Liu, P. L.; Liu, Q.; Liu, S. B.; Liu, X.; Liu, Y. B.; Liu, Z. A.; Liu, Zhiqiang; Liu, Zhiqing; Loehner, H.; Lou, X. C.; Lu, G. R.; Lu, H. J.; Lu, H. L.; Lu, J. G.; Lu, X. R.; Lu, Y.; Lu, Y. P.; Luo, C. L.; Luo, M. X.; Luo, T.; Luo, X. L.; Lv, M.; Ma, F. C.; Ma, H. L.; Ma, Q. M.; Ma, S.; Ma, T.; Ma, X. Y.; Maas, F. E.; Maggiora, M.; Malik, Q. A.; Mao, Y. J.; Mao, Z. P.; Messchendorp, J. G.; Min, J.; Min, T. J.; Mitchell, R. E.; Mo, X. H.; Mo, Y. J.; Moeini, H.; Morales, C. Morales; Moriya, K.; Muchnoi, N. Yu.; Muramatsu, H.; Nefedov, Y.; Nikolaev, I. B.; Ning, Z.; Nisar, S.; Niu, X. Y.; Olsen, S. L.; Ouyang, Q.; Pacetti, S.; Pelizaeus, M.; Peng, H. P.; Peters, K.; Ping, J. L.; Ping, R. G.; Poling, R.; Prencipe, E.; Qi, M.; Qian, S.; Qiao, C. F.; Qin, L. Q.; Qin, X. S.; Qin, Y.; Qin, Z. H.; Qiu, J. F.; Rashid, K. H.; Redmer, C. F.; Ripka, M.; Rong, G.; Ruan, X. D.; Sarantsev, A.; Schoenning, K.; Schumann, S.; Shan, W.; Shao, M.; Shen, C. P.; Shen, X. Y.; Sheng, H. Y.; Shepherd, M. R.; Song, W. M.; Song, X. Y.; Spataro, S.; Spruck, B.; Sun, G. X.; Sun, J. F.; Sun, S. S.; Sun, Y. J.; Sun, Y. Z.; Sun, Z. J.; Sun, Z. T.; Tang, C. J.; Tang, X.; Tapan, I.; Thorndike, E. H.; Toth, D.; Ullrich, M.; Uman, I.; Varner, G. S.; Wang, B.; Wang, D.; Wang, D. Y.; Wang, K.; Wang, L. L.; Wang, L. S.; Wang, M.; Wang, P.; Wang, P. L.; Wang, Q. J.; Wang, S. G.; Wang, W.; Wang, X. F.; Wang, Y. D.; Wang, Y. F.; Wang, Y. Q.; Wang, Z.; Wang, Z. G.; Wang, Z. H.; Wang, Z. Y.; Wei, D. H.; Wei, J. B.; Weidenkaff, P.; Wen, S. P.; Werner, M.; Wiedner, U.; Wolke, M.; Wu, L. H.; Wu, N.; Wu, W.; Wu, Z.; Xia, L. G.; Xia, Y.; Xiao, D.; Xiao, Z. J.; Xie, Y. G.; Xiu, Q. L.; Xu, G. F.; Xu, L.; Xu, Q. J.; Xu, Q. N.; Xu, X. P.; Xue, Z.; Yan, L.; Yan, W. B.; Yan, W. C.; Yan, Y. H.; Yang, H. X.; Yang, Y.; Yang, Y. X.; Ye, H.; Ye, M.; Ye, M. H.; Yu, B. X.; Yu, C. X.; Yu, H. W.; Yu, J. S.; Yu, S. P.; Yuan, C. Z.; Yuan, W. L.; Yuan, Y.; Zafar, A. A.; Zallo, A.; Zang, S. L.; Zeng, Y.; Zhang, B. X.; Zhang, B. Y.; Zhang, C.; Zhang, C. B.; Zhang, C. C.; Zhang, D. H.; Zhang, H. H.; Zhang, H. Y.; Zhang, J. J.; Zhang, J. L.; Zhang, J. Q.; Zhang, J. W.; Zhang, J. Y.; Zhang, J. Z.; Zhang, S. H.; Zhang, X. J.; Zhang, X. Y.; Zhang, Y.; Zhang, Y. H.; Zhang, Z. H.; Zhang, Z. P.; Zhang, Z. Y.; Zhao, G.; Zhao, J. W.; Zhao, Lei; Zhao, Ling; Zhao, M. G.; Zhao, Q.; Zhao, Q. W.; Zhao, S. J.; Zhao, T. C.; Zhao, X. H.; Zhao, Y. B.; Zhao, Z. G.; Zhemchugov, A.; Zheng, B.; Zheng, J. P.; Zheng, Y. H.; Zhong, B.; Zhou, L.; Zhou, Li; Zhou, X.; Zhou, X. K.; Zhou, X. R.; Zhou, X. Y.; Zhu, K.; Zhu, K. J.; Zhu, X. L.; Zhu, Y. C.; Zhu, Y. S.; Zhu, Z. A.; Zhuang, J.; Zou, B. S.; Zou, J. H.; Besiii Collaboration

    2014-03-01

    We report a measurement of the branching fraction B(D+→μ+νμ)=[3.71±0.19(stat)±0.06(sys)]×10-4 based on 2.92 fb-1 of data accumulated at √s =3.773 GeV with the BESIII detector at the BEPCII collider. This measurement, in conjunction with the Cabibbo-Kobayashi-Maskawa matrix element |Vcd| determined from a global Standard Model fit, implies a value for the weak decay constant fD+=(203.2±5.3±1.8) MeV. Additionally, using this branching fraction measurement together with a lattice QCD prediction for fD+, we find |Vcd|=0.2210±0.0058±0.0047. In either case, these are the most precise results for these quantities to date.

  19. Conformational distributions of N-acetyl-L-cysteine in aqueous solutions: a combined implicit and explicit solvation treatment of VA and VCD spectra.

    PubMed

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

    2012-06-18

    The conformational distributions of N-acetyl-L-cysteine (NALC) in aqueous solutions at several representative pH values are investigated using vibrational absorption (VA), UV/Vis, and vibrational circular dichroism (VCD) spectroscopy, together with DFT and molecular dynamics (MD) simulations. The experimental VA and UV/Vis spectra of NALC in water are obtained under strongly acid, neutral, and strongly basic conditions, as well as the VCD spectrum at pH 7 in D(2)O. Extensive searches are carried out to locate the most stable conformers of the protonated, neutral, deprotonated, and doubly deprotonated NALC species at the B3LYP/6-311++G(d,p) level. The inclusion of the polarizable continuum model (PCM) modifies the geometries and the relative stabilities of the conformers noticeably. The simulated PCM VA spectra show significantly better agreement with the experimental data than the gas-phase ones, thus allowing assignment of the conformational distributions and dominant species under each experimental condition. To further properly account for the discrepancies noted between the experimental and simulated VCD spectra, PCM and the explicit solvent model are utilized. MD simulations are used to aid the modelling of the NALC-(water)(N) clusters. The geometry optimization, harmonic frequency calculations, and VA and VCD intensities are computed for the NALC-(water)(3,4) clusters at the B3LYP/6-311++G(d,p) level without and with the PCM. The inclusion of both explicit and implicit solvation models at the same time provides a decisively better agreement between theory and experiment and therefore conclusive information about the conformational distributions of NALC in water and hydrogen-bonding interactions between NALC and water molecules.

  20. pH Dependent Chiroptical Properties of (1R,2R)- and (1S,2S)-trans-Cyclohexane Diesters and Diamides from VCD, ECD, and CPL Spectroscopy.

    PubMed

    Mazzeo, Giuseppe; Abbate, Sergio; Longhi, Giovanna; Castiglioni, Ettore; Boiadjiev, Stefan E; Lightner, David A

    2016-03-10

    Diesters of (1R,2R)- and (1S,2S)-cyclohexanediols and diamides of (1R,2R)- and (1S,2S)-diaminocyclohexane with p-hydroxycinnamic acid have been known for some time to exhibit intense bisignate electronic circular dichroism (ECD) spectra in CH3OH. It was also known that added NaOH causes a bathochromic shift of ∼50 nm in CH3OH, and an even higher one in DMSO. We have measured vibrational circular dichroism (VCD) spectra both for neutral compounds and in the presence of NaOH and other bases. The VCD and IR spectra in the mid-IR region for CD3OD and DMSO-d6 solution exhibit high sensitivity to the charged state for the diesters. They possess two strong bisignate features in the presence of bases in the mid-IR, which are interpreted in terms of vibrational exciton couplets, while this phenomenon is less evident in diamides. VCD allied to density functional theory (DFT) calculations allows one to shed some light on the spectral differences of diesters and diamides by studying their conformational properties. Optical rotatory dispersion (ORD) curves confirm the ECD data. Circularly polarized luminescence (CPL) data have been also acquired, which are rather intense in basified solution: the CPL spectra are monosignate and are as intense in the diester and in the diamide case.

  1. On stability, chirality measures, and theoretical VCD spectra of the chiral C58X2 fullerenes (X = N, B).

    PubMed

    Ostrowski, Sławomir; Jamróz, Michał H; Rode, Joanna E; Dobrowolski, Jan Cz

    2012-01-12

    The stability of all 23 C(58)N(2) and C(58)B(2) heterofullerenes in the singlet and triplet states was determined at the B3LYP/6-31G** level. In equilibrium mixture the achiral (1,4) C(58)N(2) isomer would be populated in ca. 95.8%, the chiral (1,16) one in ca. 3.3%, and the achiral (1,4) C(58)B(2) in 100%, whereas all triplet state isomers are less stable. Fourteen out of 23 C(58)X(2) are chiral. Four different chirality measures were calculated by our own CHIMEA program: pure geometrical, labeled, mass, and charge. Intercorrelations between the measures for all chiral compounds indicate that the pure geometrical chirality measure is unstable and should not be used in QSAR predictions of the other molecular properties, while the labeled and mass-weighted ones are promising QSAR descriptors. For each chiral C(58)N(2) molecule, some very strong VCD bands, of intensity comparable with that in the IR spectra, can serve in identification and characterization of the isomers.

  2. 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.

  3. 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.

  4. 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 C=O stretching bands.

    PubMed

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

    2015-02-05

    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 C=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.

  5. Deducing the molecular properties of zwitterionic, protonated, deprotonated, and double-deprotonated forms of L-cysteine from vibrational spectroscopy (IR, Raman, VCD) and quantum chemical calculations.

    PubMed

    Quesada-Moreno, María Mar; Avilés-Moreno, Juan Ramón; Márquez-García, A A; López-González, Juan Jesús

    2014-06-01

    The behavior of L-cysteine (C3H7NO2S, (2R)-2-amino-3-sulfanylpropanoic acid) in water at different pH values was analyzed both experimentally and theoretically. The behavior was studied at pH values of 5.21 (at this pH, L-cysteine is a zwitterionic species), 1.00 (protonated species), 8.84 (monodeprotonated species), and 13.00 (dideprotonated species). We carried out a vibrational study using nonchiroptical (IR-Raman) and chiroptical (VCD) techniques complemented by quantum chemical calculations. We adopted a dual strategy, as follows. (i) The hybrid density functionals B3LYP and M062X and the ab initio MP2 method were employed, with the same 6-311++G (d,p) basis set, in order to characterize the relative energies and structures of an extensive set of conformers of L-cysteine. The presence of water was included by utilizing the IEF-PCM implicit solvation model. (ii) The vibrational analysis was made using a chirality-sensitive using a chirality-sensitive technique (VCD) and chirality-insensitive techniques (IR, including MIR and FIR, and Raman), especially in aqueous solution. The results obtained theoretically and experimentally were compared in order to deduce the most stable structures at each pH. Moreover, for the first time, the monodeprotonated anion of L-cysteine was detected in aqueous solution by means of IR, Raman and vibrational circular dichroism (VCD). Finally, analysis of the low-frequency region using the IR and Raman techniques was shown to be a very important way to understanding the conformational preference of the zwitterionic species.

  6. Structure of the 1,4-Bis(2′-deoxyadenosin-N6-yl)-2S,3S-butanediol Intra-strand DNA Cross-link Arising from Butadiene Diepoxide in the Human N-ras Codon 61 Sequence

    PubMed Central

    Xu, Wen; Merritt, W. Keither; Nechev, Lubomir V.; Harris, Thomas M.; Harris, Constance M.; Lloyd, R. Stephen; Stone, Michael P.

    2008-01-01

    The 1,4-bis(2′-deoxyadenosin-N6-yl)-2S,3S-butanediol intra-strand DNA cross-link arises from bis-alkylation of tandem N6-dA sites in DNA by R,R-butadiene diepoxide (BDO2). The oligodeoxynucleotide 5′-d(C1G2G3A4C5X6Y7G8A9A10G11)-3′·5′-d(C12T13T14C15T16T17G18T19C20C21G22)-3′ contains the BDO2 cross-link between the second and third adenines of the codon 61 sequence (underlined) of the human N-ras protooncogene and is named the (S,S)-BD-(61-2,3) cross-link (X,Y = cross-linked adenines). NMR analysis reveals that the cross-link is oriented in the major groove of duplex DNA. Watson-Crick base pairing is perturbed at base pair X6·T17, whereas base pairing is intact at base pair Y7·T16. The cross-link appears to exist in two conformations, in rapid exchange on the NMR time scale. In the first conformation, the β-OH is predicted to form a hydrogen bond with T16 O4, whereas in the second, the β-OH is predicted to form a hydrogen bond with T17 O4. In contrast to the (R,R)-BD-(61-2,3) cross-link in the same sequence [Merritt, W.K., Nechev, L.V., Scholdberg, T.A., Dean, S.M., Kiehna, S.E., Chang, J.C., Harris, T.M., Harris, C.M., Lloyd, R.S., and Stone, M.P. (2005) Biochemistry 44, 10081–10092], the anti conformation of the two hydroxyl groups at Cβ and Cγ with respect to the Cβ-Cγ bond results in a decreased twist between base pairs X6·T17 and Y7·T16, and an approximate 10° bending of the duplex. These conformational differences may account for the differential mutagenicity of the (S,S)- and (R,R)-BD-(61-2,3) cross-links, and suggest that stereochemistry plays a role in modulating biological responses to these cross-links [Kanuri, M., Nechev, L. V., Tamura, P. J., Harris, C. M., Harris, T. M., and Lloyd, R. S. (2002) Chem. Res. Toxicol. 15, 1572–1580]. PMID:17256975

  7. 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.

  8. Experimental and ab-initio calculated vcd spectra of the first OH-stretching overtone of (1R)-(-) and (1S)-(+)-endo-BORNEOL.

    PubMed

    Gangemi, Fabrizio; Gangemi, Roberto; Longhi, Giovanna; Abbate, Sergio

    2009-04-21

    The near infrared (NIR) absorption and NIR-vibrational circular dichroism (NIR-VCD) spectra of dilute solutions of the two enantiomers of endo-borneol have been measured in the first OH-stretching overtone region (1600-1300 nm). By density functional theory (DFT) we calculate mechanical parameters, i.e. the harmonic mechanical frequency and the anharmonicity constant for the OH stretching, and anharmonic electrical parameters; i.e. the dependence on OH-bond length of atomic polar tensors and atomic axial tensors. We evaluate transition integrals for the calculations of rotational and dipole strengths by Morse anharmonic wavefunctions depending on mechanical harmonic frequencies and mechanical anharmonicity parameters that are calculated ab initio. Experimental and calculated spectra compare quite well and this fact allows us to associate differently signed NIR-VCD features with different conformational states of the OH-bond. Absorption features for the fundamental and for the second overtone of the OH stretching are also compared with experiment.

  9. 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.

  10. Self-assembly structures of 1H-indazoles in the solution and solid phases: a vibrational (IR, FIR, Raman, and VCD) spectroscopy and computational study.

    PubMed

    Avilés Moreno, J R; Quesada Moreno, M M; López González, J J; Claramunt, R M; López, C; Alkorta, I; Elguero, J

    2013-10-07

    1H-indazoles are good candidates for studying the phenomena of molecular association and spontaneous resolution of chiral compounds. Thus, because the 1H-indazoles can crystallize as dimers, trimers, or catemers, depending on their structure and the phase that they are in, the difficulty in the experimental analysis of the structure of the family of 1H-indazoles becomes clear. This difficulty leads us to contemplate several questions: How can we determine the presence of different structures of a given molecular species if they change according to the phase? Could these different structures be present in the same phase simultaneously? How can they be determined? To shed light on these questions, we outline a very complete strategy by using various vibrational spectroscopic techniques that are sensitive (VCD) and insensitive (IR, FIR, and Raman) towards the chirality, together with quantum chemical calculations.

  11. Revisiting Vibrational Circular Dichroism Spectra of (S)-(+)-Carvone and (1S,2R,5S)-(+)-Menthol Using SimIR/VCD Method.

    PubMed

    Shen, Jian; Li, Yi; Vaz, Roy; Izumi, Hiroshi

    2012-08-14

    The VCD spectra of (S)-(+)-carvone and (1S,2R,5S)-(+)-menthol are recalculated using the DFT method with extended conformation and configuration spaces. The calculated individual and averaged spectra are compared against observed ones using the previously reported similarity index, SV. It is found that the SV population forms approximately two normal distributions, depending on whether a spectrum matches the observed one or not. This statistical character can be used to estimate the error in absolute configuration (AC) assessments. To avoid erroneous AC assignments and incomplete conformation searching, it is advisible to employ a minimum |SV| of 0.2 and maximize it using conformation averaging. It is demonstrated that this approach is suitable and robust for flexible chiral molecules.

  12. Role of Side Chains in β-Sheet Self-Assembly into Peptide Fibrils. IR and VCD Spectroscopic Studies of Glutamic Acid-Containing Peptides.

    PubMed

    Tobias, Fernando; Keiderling, Timothy A

    2016-05-10

    Poly(glutamic acid) at low pH self-assembles after incubation at higher temperature into fibrils composed of antiparallel sheets that are stacked in a β2-type structure whose amide carbonyls have bifurcated H-bonds involving the side chains from the next sheet. Oligomers of Glu can also form such structures, and isotope labeling has provided insight into their out-of-register antiparallel structure [ Biomacromolecules 2013 , 14 , 3880 - 3891 ]. In this paper we report IR and VCD spectra and transmission electron micrograph (TEM) images for a series of alternately sequenced oligomers, Lys-(Aaa-Glu)5-Lys-NH2, where Aaa was varied over a variety of polar, aliphatic, or aromatic residues. Their spectral and TEM data show that these oligopeptides self-assemble into different structures, both local and morphological, that are dependent on both the nature of the Aaa side chains and growth conditions employed. Such alternate peptides substituted with small or polar residues, Ala and Thr, do not yield fibrils; but with β-branched aliphatic residues, Val and Ile, that could potentially pack with Glu side chains, these oligopeptides do show evidence of β2-stacking. By contrast, for Leu, with longer side chains, only β1-stacking is seen while with even larger Phe side chains, either β-form can be detected separately, depending on preparation conditions. These structures are dependent on high temperature incubation after reducing the pH and in some cases after sonication of initial fibril forms and reincubation. Some of these fibrillar peptides, but not all, show enhanced VCD, which can offer evidence for formation of long, multistrand, often twisted structures. Substitution of Glu with residues having selected side chains yields a variety of morphologies, leading to both β1- and β2-structures, that overall suggests two different packing modes for the hydrophobic side chains depending on size and type.

  13. Electrical and mechanical anharmonicities from NIR-VCD spectra of compounds exhibiting axial and planar chirality: the cases of (S)-2,3-pentadiene and methyl-d(3) (R)- and (S)-[2.2]paracyclophane-4-carboxylate.

    PubMed

    Abbate, Sergio; Longhi, Giovanna; Gangemi, Fabrizio; Gangemi, Roberto; Superchi, Stefano; Caporusso, Anna Maria; Ruzziconi, Renzo

    2011-10-01

    The IR and Near infrared (NIR) vibrational circular dichroism (VCD) spectra of molecules endowed with noncentral chirality have been investigated. Data for fundamental, first, and second overtone regions of (S)-2,3-pentadiene, exhibiting axial chirality, and methyl-d(3) (R)- and (S)-[2.2]paracyclophane-4-carboxylate, exhibiting planar chirality have been measured and analyzed. The analysis of NIR and IR VCD spectra was based on the local-mode model and the use of density functional theory (DFT), providing mechanical and electrical anharmonic terms for all CH-bonds. The comparison of experimental and calculated spectra is satisfactory and allows one to monitor fine details in the asymmetric charge distribution in the molecules: these details consist in the harmonic frequencies, in the principal anharmonicity constants, in both the atomic polar and axial tensors and in their first and second derivatives with respect to the CH-stretching coordinates.

  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. Is β-homo-proline a pseudo-γ-turn forming element of β-peptides? An IR and VCD spectroscopic study on Ac-β-HPro-NHMe in cryogenic matrices and solutions.

    PubMed

    Góbi, Sándor; Knapp, Krisztina; Vass, Elemér; Majer, Zsuzsanna; Magyarfalvi, Gábor; Hollósi, Miklós; Tarczay, György

    2010-11-07

    In order to test the pseudo-γ-turn forming capability of β-homo-proline (β(3)-HPro) 2-[(2S)-1-acetylpyrrolidin-2-yl]-N-methylacetamide (Ac-β(3)-HPro-NHMe) was synthesized and its potential energy landscape was investigated by infrared (IR) and vibrational circular dichroism (VCD) spectroscopy combined with density functional calculations. Based upon a comparison between experimental and computed spectra three different pseudo-γ-turn-like trans conformers and a cis conformer were identified in low-temperature Ar and Kr matrices. The computations in agreement with the observations reveal that, in contrast to its α-Pro analogue, the room-temperature abundance of the cis conformer is significant, falling above 10% in the isolated phase. Furthermore, solution-phase vibrational spectra and computations show that the cis conformer is predominant in polar solvents. This result indicates that β(3)-HPro is significantly less apt to form pseudo-γ-turns when compared to the γ-turn forming tendency of α-proline. The present study also shows that the interpretation of solution-phase VCD spectra of flexible molecules should be done with extra caution.

  16. Study of stereoselective interactions of carbamoylated quinine and quinidine with 3,5-dinitrobenzoyl α-amino acids using VCD spectroscopy in the region of C−H stretching vibrations.

    PubMed

    Julínek, Ondřej; Lindner, Wolfgang; Urbanová, Marie

    2011-04-01

    The stereoselective complexation of tert-butylcarbamoyl quinine and tert-butylcarbamoyl quinidine selectors (SOs) with 3,5-dinitrobenzoyl (DNB) derivatives of D- and L-alpha amino acids (DNB-Ala, DNB-Val, DNB-Leu, and DNB-Ile) as well as achiral DNB-Gly has been studied by vibrational circular dichroism (VCD) spectroscopy in the spectral region of C−H stretching vibrations. All the complexes of SOs and sterically compatible enantiomers of derivatized amino acid selectands (SAs) showed induced circular dichroism (ICD) bands in the region of aromatic C−H stretching vibrations, indicating the occurrence of a π-π interaction between the aromatic moieties of SA and SO. To our knowledge, this is the first report in which a π-π interaction was observed by VCD spectroscopy in this spectral region. No ICD bands were disclosed in the spectra of the sterically incompatible SA and SO complexes. The spectral pattern in the region of aliphatic C−H stretching vibrations showed interaction-induced conformational adaptations in sterically favorable SA and SO complexes. No such spectral changes were observed for any of the sterically incompatible complexes. The DNB-Gly complexes exhibited spectral patterns similar to those observed for sterically favorable pairs of SOs and chiral SAs.

  17. 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.

  18. Supramolecular organization of perfluorinated 1H-indazoles in the solid state using X-ray crystallography, SSNMR and sensitive (VCD) and non sensitive (MIR, FIR and Raman) to chirality vibrational spectroscopies.

    PubMed

    Quesada-Moreno, María M; Avilés-Moreno, Juan Ramón; López-González, Juan Jesús; Jacob, Kane; Vendier, Laure; Etienne, Michel; Alkorta, Ibon; Elguero, José; Claramunt, Rosa M

    2017-01-04

    1H-Indazole derivatives exhibit a remarkable property since some of them form chiral supramolecular structures starting from achiral monomers. The present work deals with the study of three perfluorinated 1H-indazoles that resolve spontaneously as conglomerates. These conglomerates can contain either a pure enantiomer (one helix) or a mixture of both enantiomers (both helices) with an enantiomeric excess (e.e.) of one of them. The difficulty of the structural analysis of these types of compounds is thus clear. We outline a complete strategy to determine the structures and configurations (M or P helices) of the enantiomers (helices) forming the conglomerates of these perfluorinated 1H-indazoles based on X-ray crystallography, solid state NMR spectroscopy and different solid state vibrational spectroscopies that are either sensitive (VCD) or not (FarIR, IR and Raman) to chirality, together with quantum chemical calculations (DFT).

  19. Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions.

    PubMed

    McAnaw, Amelia; Lopez, Maria Elena; Ellis, David; Rosair, Georgina M; Welch, Alan J

    2014-04-07

    The isolation of six isomeric, low-symmetry, dicobaltacarboranes with bicapped hexagonal antiprismatic cage structures, always in low yield, is described from reactions in which 13-vertex cobaltacarborane anions and sources of cobalt-containing cations were present. The vertex-to-centroid distance (VCD) and boron-H distance (BHD) methods are used to locate the correct C atom positions in the cages, thus allowing the compounds to be identified as 1,13-Cp2-1,13,2,10-closo-Co2C2B10H12 (1), 1,8-Cp2-3-OEt-1,8,2,10-closo-Co2C2B10H11 (2), 1,13-Cp2-1,13,2,9-closo-Co2C2B10H12 (3), 1,8-Cp2-1,8,2,4-closo-Co2C2B10H12 (4), 1,13-Cp2-1,13,2,4-closo-Co2C2B10H12 (5) and 1,8-Cp2-1,8,2,5-closo-Co2C2B10H12 (6). It is shown that a common alternative method of cage C atom identification, using refined (as B) U(eq) values, does not work well, at least in these cases. Having identified the correct isomeric forms of the six dicobaltacarboranes, their syntheses are tentatively rationalised in terms of the direct electrophilic insertion of a {CpCo(+)} fragment into [CpCoC2B10](-) anions and it is demonstrated that compounds 1, 4, 5 and 6 can be successfully prepared by deliberately performing such reactions.

  20. Analysis of second-harmonic-generation microscopy in a mouse model of ovarian carcinoma.

    PubMed

    Watson, Jennifer M; Rice, Photini F; Marion, Samuel L; Brewer, Molly A; Davis, John R; Rodriguez, Jeffrey J; Utzinger, Urs; Hoyer, Patricia B; Barton, Jennifer K

    2012-07-01

    Second-harmonic-generation (SHG) imaging of mouse ovaries ex vivo was used to detect collagen structure changes accompanying ovarian cancer development. Dosing with 4-vinylcyclohexene diepoxide and 7,12-dimethylbenz[a]anthracene resulted in histologically confirmed cases of normal, benign abnormality, dysplasia, and carcinoma. Parameters for each SHG image were calculated using the Fourier transform matrix and gray-level co-occurrence matrix (GLCM). Cancer versus normal and cancer versus all other diagnoses showed the greatest separation using the parameters derived from power in the highest-frequency region and GLCM energy. Mixed effects models showed that these parameters were significantly different between cancer and normal (P<0.008). Images were classified with a support vector machine, using 25% of the data for training and 75% for testing. Utilizing all images with signal greater than the noise level, cancer versus not-cancer specimens were classified with 81.2% sensitivity and 80.0% specificity, and cancer versus normal specimens were classified with 77.8% sensitivity and 79.3% specificity. Utilizing only images with greater than of 75% of the field of view containing signal improved sensitivity and specificity for cancer versus normal to 81.5% and 81.1%. These results suggest that using SHG to visualize collagen structure in ovaries could help with early cancer detection.

  1. Analysis of second-harmonic-generation microscopy in a mouse model of ovarian carcinoma

    PubMed Central

    Watson, Jennifer M.; Rice, Photini F.; Marion, Samuel L.; Brewer, Molly A.; Davis, John R.; Rodriguez, Jeffrey J.; Utzinger, Urs; Hoyer, Patricia B.

    2012-01-01

    Abstract. Second-harmonic-generation (SHG) imaging of mouse ovaries ex vivo was used to detect collagen structure changes accompanying ovarian cancer development. Dosing with 4-vinylcyclohexene diepoxide and 7,12-dimethylbenz[a]anthracene resulted in histologically confirmed cases of normal, benign abnormality, dysplasia, and carcinoma. Parameters for each SHG image were calculated using the Fourier transform matrix and gray-level co-occurrence matrix (GLCM). Cancer versus normal and cancer versus all other diagnoses showed the greatest separation using the parameters derived from power in the highest-frequency region and GLCM energy. Mixed effects models showed that these parameters were significantly different between cancer and normal (P<0.008). Images were classified with a support vector machine, using 25% of the data for training and 75% for testing. Utilizing all images with signal greater than the noise level, cancer versus not-cancer specimens were classified with 81.2% sensitivity and 80.0% specificity, and cancer versus normal specimens were classified with 77.8% sensitivity and 79.3% specificity. Utilizing only images with greater than of 75% of the field of view containing signal improved sensitivity and specificity for cancer versus normal to 81.5% and 81.1%. These results suggest that using SHG to visualize collagen structure in ovaries could help with early cancer detection. PMID:22894485

  2. Flanking sequences modulate diepoxide and mustard cross-linking efficiencies at the 5'-GNC site.

    PubMed

    Sawyer, Gregory A; Frederick, Elizabeth D; Millard, Julie T

    2004-08-01

    Diepoxybutane, diepoxyoctane, and mechlorethamine are cytotoxic agents that induce interstrand cross-links between the N7 positions of deoxyguanosine residues on opposite strands of the DNA duplex preferentially at 5'-GNC sequences. We have systematically varied the identity of either the base 5' to the cross-linked deoxyguanosine residues or the intervening base pair to determine flanking sequence effects on cross-linking efficiency. We used synthetic DNA oligomers containing four 5'-N(1)GN(2)C sites that varied either N(1) or N(2). Interstrand cross-links were purified through denaturing polyacrylamide gel electrophoresis and then subjected to piperidine cleavage. The amount of cleavage at each deoxyguanosine residue, representative of cross-linking efficiency at that site, was determined by sequencing gel analysis. Our data suggest that cross-linking efficiency varies with the identity of N(1) similarly (purines > pyrimidines) for diepoxybutane, diepoxyoctane, and mechlorethamine but that the effects of N(2) differ for the three compounds.

  3. 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

  4. Vibrational circular dichroism (VCD), VCD exciton coupling, and X-ray determination of the absolute configuration of an α,β-unsaturated germacranolide.

    PubMed

    Sánchez-Castellanos, Mariano; Bucio, María A; Hernández-Barragán, Angelina; Joseph-Nathan, Pedro; Cuevas, Gabriel; Quijano, Leovigildo

    2015-03-01

    The absolute configuration of was deduced by vibrational circular dichroism together with the evaluation of the Flack and Hooft X-ray parameters. Vibrational circular dichroism exciton coupling, using the carbonyl group signals, confirmed the absolute configuration of . In addition, sodium borohydride reduction of the 11,13-double bond of 6-epi-desacetyllaurenobiolide () yields an almost equimolecular mixture of C11 epimers, while reduction of the same double bond of 6-epi-laurenobiolide () provided almost exclusively the (11S) diastereoisomer .

  5. 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.

  6. The VA, VCD, Raman and ROA spectra of tri-L-serine in aqueous solution.

    PubMed

    Jürgensen, V Würtz; Jalkanen, K

    2006-02-22

    The structures of one conformer of the nonionic neutral and zwitterionic species of L-serinyl L-serinyl L-serine (SSS or tri-L-serine), together with its cationic and anionic species and the capped N-acetyl tri-L-serine N'-methylamide analog were optimized with density functional theory with the Becke 3LYP hybrid exchange correlation (XC) functional and the PW91 GGA XC functional and the 6-31G* and aug-cc-pVDZ basis sets. Subsequently, the vibrational absorption, vibrational circular dichroism, Raman and Raman optical activity spectra were simulated in order to compare them to experimentally measured spectra. In addition, we compare to previously reported studies for both structural determination and spectral simulations and measurements. A comparison of the various ways to treat the effects of the environment and solvation on both the structure and the spectral properties is thoroughly investigated for one conformer, with the goal to determine which level of theory is appropriate to use in the systematic search of the conformational space. In addition, the effects of the counterion, here Cl- anion, are also investigated. Here we present the current state of the art in nanobiology, where the latest methods in experimental and theoretical vibrational spectroscopy are used to gain useful information about the coupling of the nuclear, electronic and magnetic degrees of freedom and structure of tri-L-serine and its capped peptide analog with the environment.

  7. Inhibition of macrophage activation by the myxoma virus M141 protein (vCD200).

    PubMed

    Zhang, Leiliang; Stanford, Marianne; Liu, Jia; Barrett, Catherine; Jiang, Lei; Barclay, A Neil; McFadden, Grant

    2009-09-01

    The M141 protein of myxoma virus (MYXV) is a viral CD200 homolog (also called vOX-2) that inhibits macrophage activation in infected rabbits. Here, we show that murine myeloid RAW 264.7 cells became activated when infected with MYXV in which the M141 gene was deleted (vMyx-M141KO) but not with the parental wild-type MYXV. Moreover, transcript and protein levels of tumor necrosis factor and granulocyte colony-stimulating factor were rapidly upregulated in an NF-kappaB-dependent fashion in the RAW 264.7 cells infected with vMyx-M141KO. M141 protein is present in the virion and counteracts this NF-kappaB activation pathway upon infection with the wild-type MYXV. Our data suggest that upregulation of these classic macrophage-related proinflammatory cytokine markers following infection of myeloid cells with the M141-knockout MYXV is mediated via the rapid activation of the cellular NF-kappaB pathway.

  8. Atomistic modeling of IR action spectra under circularly polarized electromagnetic fields: toward action VCD spectra.

    PubMed

    Calvo, Florent

    2015-03-01

    The nonlinear response and dissociation propensity of an isolated chiral molecule, camphor, to a circularly polarized infrared laser pulse was simulated by molecular dynamics as a function of the excitation wavelength. The results indicate similarities with linear absorption spectra, but also differences that are ascribable to dynamical anharmonic effects. Comparing the responses between left- and right-circularly polarized pulses in terms of dissociation probabilities, or equivalently between R- and S-camphor to a similarly polarized pulse, we find significant differences for the fingerprint C = O amide mode, with a sensitivity that could be sufficient to possibly enable vibrational circular dichroism as an action technique for probing molecular chirality and absolute conformations in the gas phase.

  9. Synthesis and anti-HIV activity of lupane and olean-18-ene derivatives. Absolute configuration of 19,20-epoxylupanes by VCD.

    PubMed

    Gutiérrez-Nicolás, Fátima; Gordillo-Román, Bárbara; Oberti, Juan C; Estévez-Braun, Ana; Ravelo, Angel G; Joseph-Nathan, Pedro

    2012-04-27

    Lupane triterpenoids 2 and 5-12 and oleanene derivatives 13 and 14 were prepared from lupeol (1), betulin (3), and germanicol (4). They were tested for anti-HIV activity, and some structure-activity relationships were outlined. The 20-(S) absolute configuration of epoxylupenone (8) was assessed by comparison of the observed and DFT-calculated vibrational circular dichroism spectra. The CompareVOA algorithm was employed to support the C-20 configuration assignment. The 20,29 double bond in lupenone (2) and 3-epilupeol (15) was stereoselectively epoxidized to produce 20-(S)-8 and 20-(S)-16, respectively, an assignment in agreement with their X-ray diffraction structures.

  10. Vibrational circular dichroism (VCD) chiral assignment of atropisomers: application to γ-aminobutyric acid (GABA) modulators designed as potential anxiolytic drugs.

    PubMed

    Pivonka, Don E; Wesolowski, Steven S

    2013-04-01

    Atropisomers exist when axial chirality is present as a result of conformationally restricted rotation around a single bond. The interconversion rate of the individual atropisomers is critical to the assessment of chiral stability of a drug throughout scale-up, development, production, and storage as well as in vivo pharmacokinetics. We describe the application of vibrational circular dichroism spectroscopy coupled with quantum mechanics simulations to assign the absolute axial chirality and measure the racemization half-life of a series of potential anxiolytic drugs that act as γ-aminobutyric acid modulators.

  11. Data of aromatase inhibitors alone and in combination with raloxifene on microarchitecture of lumbar vertebrae and strength test in femoral diaphysis of VCD treated ovotoxic mice.

    PubMed

    Kalam, Abul; Talegaonkar, Sushama; Vohora, Divya

    2017-02-01

    Currently, the third generation aromatase inhibitors are the drugs of choice for treatment of early and advanced breast cancer in postmenopausal women. The negative impact of these drugs on bone health is the significant limiting factor during this therapy. Here we report the effect of two aromatase inhibitors viz. letrozole and exemestane alone and in combination with raloxifene on lumbar vertebrae and femoral diaphysis after one month of treatment but no discernible effects were observed on bone when tested by micro CT and strength test except in trabecular number which was reduced in lumbar vertebrae following letrozole and exemestane. Further studies with letrozole and exemestane should be done at higher doses for longer duration of time to check whether effects are observed in other parameters as well. The data is an extension of our published work in Mol. Cell Endocrinology (A. Kalam, S. Talegaonkar, D. Vohora, 2017) [1] describing letrozole-induced bone loss on femoral epiphysis and its reversal by raloxifene.

  12. Structural determination of molecular stereochemistry using VCD spectroscopy and a conformational code: absolute configuration and solution conformation of a chiral liquid pesticide, (R)-(+)-malathion.

    PubMed

    Izumi, Hiroshi; Ogata, Atsushi; Nafie, Laurence A; Dukor, Rina K

    2009-01-01

    The absolute configuration and solution conformation of (R)-(+)-malathion were determined by using vibrational circular dichroism spectroscopy and a fragment-conformational search with a recently published conformational code. The determination of molecular stereochemistry was carried out without a conformational search using molecular mechanics calculations. Density functional theory calculations of the fragments of (R)-malathion, ethyl propionate, (R)-ethyl 2-(methylthio)propanoate, (R)-diethyl 2-(methylthio)succinate, and O,O,S-trimethyl phosphorodithioate were carried out, and the principal conformational features of the fragments were profiled. This fragment-conformational search reduces the time needed for the selection of the predominant conformations for (R)-malathion and significantly improves the accuracy of the determination of absolute configuration.

  13. An Analysis of Cryptographically Significant Boolean Functions With High Correlation Immunity by Reconfigurable Computer

    DTIC Science & Technology

    2010-12-01

    USEVCS = yes # YES or yes to use vcs instead of vcsi #VCSDUMP = yes # YES or yes to generate vcd + trace dump...MDLDUMP = yes # YES or yes to generate vcd trace dump # ----------------------------------- # No modifications are required below

  14. Computing the Algebraic Immunity of Boolean Functions on the SRC-6 Reconfigurable Computer

    DTIC Science & Technology

    2012-03-01

    yes # YES or yes to use vcs instead of vcsi #VCSDUMP = yes # YES or yes to generate vcd + trace dump...YES or yes to generate vcd trace dump # ----------------------------------- # No modifications are required below

  15. An Analysis of Bent Function Properties Using the Transeunt Triangle and the SRC-6 Reconfigurable Computer

    DTIC Science & Technology

    2009-09-01

    USEVCS = yes # YES or yes to use vcs instead of vcsi #VCSDUMP = yes # YES or yes to generate vcd ...modelsim GUI interface #MDLDUMP = yes # YES or yes to generate vcd trace dump # ----------------------------------- # No modifications are

  16. Discovery of Bent Functions Using the Fast Walsh Transform

    DTIC Science & Technology

    2010-12-01

    vcsi #VCSDUMP = yes # YES or yes to generate vcd + trace dump # ----------------------------------- # MODELSIM simulation settings # (Set as...vcs/vcsi #USEMDLGUI = yes # YES or yes to use modelsim GUI interface #MDLDUMP = yes # YES or yes to generate vcd trace dump...YES or yes to generate vcd + trace dump # ----------------------------------- # MODELSIM simulation settings # (Set as needed, otherwise just leave

  17. Vocal cord dysfunction, gastroesophageal reflux disease, and nonallergic rhinitis.

    PubMed

    Balkissoon, Ron

    2007-01-01

    VCD is often mistaken for asthma and can lead to treatment with corticosteroids and the development of significant side effects. Early and correct diagnosis will avert significant iatrogenic complications. For many individuals, the role of postnasal drip and GERD in the pathogenesis of VCD is central, as they are often associated with VCD and likely lead to increased laryngopharyngeal sensitivity and hyperreactivity. Much needs to be further elucidated in terms of the underlying pathogenesis of VCD. Management of VCD requires identification and treatment of underlying disorders and referral to speech therapists that can teach techniques of throat relaxation, cough suppression, and throat clearing suppression.

  18. Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

    PubMed

    Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

    2014-06-01

    A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates.

  19. Developing a Corrective Action Simulator to Support Decision Making Research and Training

    DTIC Science & Technology

    2008-05-01

    shall produce DIS Entity State PDUs for the ground entities. 2.3 The TGM shall support a Virtual Character Display ( VCD ). 2.3.1 [DELETED] 2.3.2...The TGM VCD shall load a 3-D environment which contains an AWACS-like interior. 2.3.2.1 The TGM VCD AWACS-like interior shall include at least two...Weapons Director (WD) positions/work areas. 2.3.3 The TGM VCD shall support the WD consoles drawn with textures. 2.3.3.1 The TGM VCD WD console

  20. The connection between robustness angles and dissymmetry factors in vibrational circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Longhi, Giovanna; Tommasini, Matteo; Abbate, Sergio; Polavarapu, Prasad L.

    2015-10-01

    To analyze vibrational circular dichroism (VCD) spectra the angle between the electric and magnetic dipole transition moments was introduced as robustness index. We demonstrate that VCD for each normal mode can be made robust by a suitable translation of the coordinate system origin to a robust point. Normal modes differ in how VCD band robustness varies under translations from these respective robust points. It is shown that variation in robustness of a VCD band depends on a parameter inversely proportional to the dissymmetry factor g. Thus, robustness varies slowly for VCD bands with large dissymmetry factors and vice versa.

  1. 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.

  2. VASCULAR CLOSURE DEVICE FAILURE IN CONTEMPORARY PRACTICE

    PubMed Central

    Vidi, Venkatesan D.; Matheny, Michael E.; Govindarajulu, Usha S.; Normand, Sharon-Lise T.; Robbins, Susan L.; Agarwal, Vikram V.; Bangalore, Sripal; Resnic, Frederic S.

    2012-01-01

    Objectives To assess the frequency and predictors of vascular closure device (VCD) deployment failure, and its association with vascular complications of three commonly used VCDs. Background VCDs are commonly used following percutaneous coronary intervention (PCI) on the basis of studies demonstrating reduced time to ambulation, increased patient comfort, and possible reduction in vascular complications as compared to manual compression. However, limited data are available on the frequency and predictors of VCD failure, and the association of deployment failure with vascular complications. Methods From a de-identified dataset provided by Massachusetts Department of Health, 23,813 consecutive interventional coronary procedures that used either a collagen plug-based (n=18,533) or nitinol clip-based (n=2,284) or suture-based (n=2,996) VCD between 06/2005 and 12/2007 were identified. We defined VCD failure as unsuccessful deployment or failure to achieve immediate access site hemostasis. Results Among 23,813 procedures, VCD failed in 781 (3.3%) procedures (2.1% of collagen plug-based, 6.1% of suture-based, 9.5% of nitinol clip-based). Patients with VCD failure had excess risk of ‘any’ (7.7% versus 2.8%; P<0.001), major (3.3% versus 0.8%; P<0.001), or minor (5.8% versus 2.1%; P<0.001) vascular complications compared with successful VCD deployment. In a propensity-score adjusted analysis, when compared with collagen plug-based VCD (Reference OR =1.0), nitinol clip-based VCD had 2-fold increased risk (OR 2.0, 95% CI: 1.8–2.3, p<0.001) and suture-based VCD had 1.25-fold increased risk (OR 1.25, 95% CI: 1.2–1.3, p<0.001) for VCD failure. VCD failure was a significant predictor of subsequent vascular complications for both collagen plug-based VCD and nitinol clip-based VCD, but not for suture-based VCD. Conclusion VCD failure rates vary depending upon the types of VCD used and are associated with significantly higher vascular complications as compared to deployment

  3. Vocal cord dysfunction diagnosed by four-dimensional dynamic volume computed tomography in patients with difficult-to-treat asthma: A case series.

    PubMed

    Cheng, Wei-Tso; Chen, Huan-Wen; Su, I-Hao; Fang, Ji-Tseng; Kuo, Han-Pin; Huang, Chien-Da

    2015-12-01

    Patients with asthma may also have vocal cord dysfunction (VCD), which leads to poor control of the asthma. Once patients are diagnosed with difficult-to-treat asthma with poor control, VCD should be excluded or treated accordingly. The gold standard for diagnosis of VCD is to perform a laryngoscopy. However, this procedure is invasive and may not be suitable for patients with difficult-to-treat asthma. Four-dimensional (4D) dynamic volume computed tomography (CT) is a noninvasive method for quantification of laryngeal movement, and can serve as an alternative for the diagnosis of VCD. Herein, we present a series of five cases with difficult-to-treat asthma patients who were diagnosed with VCD by 4D dynamic volume CT. Clinicians should be alert to the possibility of VCD when poor control is noted in patients with asthma. Early diagnosis by noninvasive 4D dynamic volume CT can decrease excessive doses of inhaled corticosteroids.

  4. Effectiveness of brain-based learning and animated cartoons for enhancing healthy habits among school children in Khon Kaen, Thailand.

    PubMed

    Banchonhattakit, Pannee; Duangsong, Rujira; Muangsom, Niramon; Kamsong, Theppamon; Phangwan, Krittiya

    2015-03-01

    The objective of this study was to investigate the effectiveness of brain-based learning (BBL) and animated cartoons on video compact discs (VCDs) in enhancing the healthy habits of school children. A representative sample of 1085 school children in the first through the third grades at 16 schools was selected by multistage random sampling. Knowledge of healthy habits and self-reported adoption of practices were assessed by a questionnaire. BBL and VCD, either combined or as single-intervention techniques, led to improved knowledge and practice of healthy behavior, whereas conventional teaching did not. As a single-intervention technique, BBL on its own led to a greater improvement in healthy practices than VCD, but the addition of BBL to VCD made no difference, and there was no difference between BBL and VCD in terms of improvements in knowledge. In conclusion, both BBL and VCD are effective, but VCD requires fewer resources. Recommendations are made for further research.

  5. Implementation Challenges for DoD Logistics Enterprise Resource Planning IT Systems

    DTIC Science & Technology

    2010-09-01

    Block 1 Program Schedule Comparisons CY2009 FY2005 FY2006 FY2007 FY2010 CY2005 MS A ADM (23 July 04) MS B ADM (8 Jun 07) Build / SI DT / VCD Field...Enterprise Release to III MEF & Selected I/II MEF Units FOC Gov DT Build / SI DT / VCD Gov DT&E / FOT&E / VCD MS C ADM IOC OTGov DT Prep FUE VC D

  6. JPRS Report, Science & Technology, Manned Spaceflight Technology Symposium.

    DTIC Science & Technology

    2007-11-02

    absorption and membrane pro- cesses Phase change process MF (Multi- filtration) HF (Hyper- filtration) VCD (Vapor TIMES (Thermo...and molecules) treatment of low- contaminated water Process of Same as for highly contain- VCD inated water like urine htir pre- CfSI- inq...the reverse osmosis membrane method (HF method) is employed, while for highly contaminated urine, the VCD method, a distillation method, and the

  7. 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.

  8. 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.

  9. Thermodynamical vibronic coupling constant and density: Chemical potential and vibronic coupling in reactions

    NASA Astrophysics Data System (ADS)

    Sato, Tohru; Haruta, Naoki; Tanaka, Kazuyoshi

    2016-05-01

    Vibronic coupling constant (VCC) and density (VCD) defined for a pure state, which have been successfully applied for reactions of fullerenes and nanographenes as reactivity indices, are extended for a mixed state. The extended VCC and VCD, thermodynamical vibronic coupling constant (ThVCC) and density (ThVCD), are formulated in the finite-temperature grand-canonical ensemble. ThVCD can be applied for charge transfer of a fractional number of electron. Based on the total differential of chemical potential, the relationship between chemical potential, absolute hardness, and vibronic coupling in a bimolecular reaction is discussed.

  10. Improved mechanical properties of A 508 class 3 steel for nuclear pressure vessel through steelmaking

    SciTech Connect

    Kim, J.T.; Kwon, H.K.; Kim, K.C.; Kim, J.M.

    1997-12-31

    The present work is concerned with the steelmaking practices which improve the mechanical properties of the A 508 class 3 steel for reactor pressure vessel. Three kinds of steelmaking practices were applied to manufacture the forged heavy wall shell for reactor pressure vessel, that is, the vacuum carbon deoxidation (VCD), modified VCD containing aluminum and silicon-killing. The segregation of the chemical elements through the thickness was quite small so that the variations of the tensile properties at room temperature were small and the anisotropy of the impact properties was hardly observed regardless of the steelmaking practices. The Charpy V-notch impact properties and the reference nil-ductile transition temperature by drop weight test were significantly improved by the modified VCD and silicon-killing as compared with those of the steel by VCD. Moreover, the plane strain fracture toughness values of the materials by modified VCD and silicon-killing practices was much higher than those of the steel by VCD. These were resulted from the fining of austenite grain size. It was observed that the grain size was below 20 {micro}m (ASTM No. 8.5) when using the modified VCD and silicon-killing, compared to 50 {micro}m (ASTM No. 7.0) when using VCD.

  11. Link Performance Analysis of a Ship-to-Ship Laser Communication System

    DTIC Science & Technology

    2012-03-01

    ASSUMPTIONS In this search-and-rescue mission, video images and voice commands are transmitted at 1.5 Mbps (video compact disc ( VCD ) quality using moving...fro the ships at 1.5 Mbps (video compact disc ( VCD ) quality using MPEG1 compression) with a BER. The SNR required for achieving the desired voice

  12. BADAL: A Culture of Revenge, The Impact of Collateral Damage on Taliban Insurgency

    DTIC Science & Technology

    2008-03-01

    against the near enemy. Coupled with 108 Parvez’s Dear Guest, VCD , 2004; Waziristan, Pakistan: Ummat...Parvez’s Dear Guest. VCD .2004; Waziristan, Pakistan: Ummat Studio, 2004. Petrou, Michael. “Barbarians at the Gate.” Maclean’s, August 13, 2007

  13. The Circular Pipeline: Achieving Higher Throughput in the Search for Bent Functions

    DTIC Science & Technology

    2010-09-01

    vcs instead of vcsi #VCSDUMP = yes # YES or yes to generate vcd + trace dump # ----------------------------------- # MODELSIM simulation...modelsim instead of vcs/vcsi #USEMDLGUI = yes # YES or yes to use modelsim GUI interface #MDLDUMP = yes # YES or yes to generate vcd

  14. Flexible moldable conductive current-limiting materials

    DOEpatents

    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.

  15. 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 ...

  16. Practical management: vocal cord dysfunction in athletes.

    PubMed

    Wilson, John J; Wilson, Erin M

    2006-07-01

    Vocal cord dysfunction (VCD) is characterized by paradoxical adduction of the vocal folds during inhalation, and occasionally upon exhalation, resulting in extrathoracic airflow obstruction. Sports medicine professionals must have a high index of suspicion for VCD when acute respiratory symptoms occur so that prompt evaluation and use of appropriate specialists results in an accurate and timely diagnosis. Many factors have been implicated in the pathophysiology of VCD, including laryngeal irritants, psychogenic and neurogenic causes. The diagnosis and management of VCD involves a variety of specialties including pulmonology, otolaryngology, speech-language pathology, allergy and immunology, and psychologic management as appropriate. The mainstay of treatment remains behavioral management guided by a medical speech-language pathologist, as well as pharmacologic management for VCD triggers.

  17. Systematic approach to conformational sampling for assigning absolute configuration using vibrational circular dichroism.

    PubMed

    Sherer, Edward C; Lee, Claire H; Shpungin, Joseph; Cuff, James F; Da, Chenxiao; Ball, Richard; Bach, Richard; Crespo, Alejandro; Gong, Xiaoyi; Welch, Christopher J

    2014-01-23

    Systematic methods that speed-up the assignment of absolute configuration using vibrational circular dichrosim (VCD) and simplify its usage will advance this technique into a robust platform technology. Applying VCD to pharmaceutically relevant compounds has been handled in an ad hoc fashion, relying on fragment analysis and technical shortcuts to reduce the computational time required. We leverage a large computational infrastructure to provide adequate conformational exploration which enables an accurate assignment of absolute configuration. We describe a systematic approach for rapid calculation of VCD/IR spectra and comparison with corresponding measured spectra and apply this approach to assign the correct stereochemistry of nine test cases. We suggest moving away from the fragment approach when making VCD assignments. In addition to enabling faster and more reliable VCD assignments of absolute configuration, the ability to rapidly explore conformational space and sample conformations of complex molecules will have applicability in other areas of drug discovery.

  18. 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.

  19. 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.

  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

    2016-10-01

    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].

  1. Structures of plant viruses from vibrational circular dichroism.

    PubMed

    Shanmugam, Ganesh; Polavarapu, Prasad L; Kendall, Amy; Stubbs, Gerald

    2005-08-01

    Vibrational circular dichroism (VCD) spectra in the amide I and II regions have been measured for viruses for the first time. VCD spectra were recorded for films prepared from aqueous buffer solutions and also for solutions using D(2)O buffers at pH 8. Investigations of four filamentous plant viruses, Tobacco mosaic virus (TMV), Papaya mosaic virus, Narcissus mosaic virus (NMV) and Potato virus X (PVX), as well as a deletion mutant of PVX, are described in this paper. The film VCD spectra of the viruses clearly revealed helical structures in the virus coat proteins; the nucleic acid bases present in the single-stranded RNA could also be characterized. In contrast, the solution VCD spectra showed the characteristic VCD bands for alpha-helical structures in the coat proteins but not for RNA. Both sets of results clearly indicated that the coat protein conformations are dominated by helical structures, in agreement with earlier reports. VCD results also indicated that the coat protein structures in PVX and NMV are similar to each other and somewhat different from that of TMV. The present study demonstrates the feasibility of measuring VCD spectra for viruses and extracting structural information from these spectra.

  2. 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.

  3. Fourier transform vibrational circular dichroism of small pharmaceutical molecules

    NASA Astrophysics Data System (ADS)

    Long, Fujin; Freedman, Teresa B.; Nafie, Laurence A.

    1998-06-01

    Fourier transform vibrational circular dichroism (FT-VCD) spectra of the small pharmaceutical molecules propanolol, ibuprofen and naproxen have been measured in the hydrogen stretching and mid-infrared regions to obtain information on solution conformation and to identify markers for absolute configuration determination. Ab initio molecular orbital calculations of low energy conformations, vibrational frequencies and VCD intensities for fragments of the drugs were utilized in interpreting the spectra. Features characteristic of five conformers of propranolol were identified. The weak positive CH stretching VCD signal in ibuprofen and naproxen is characteristic of the S-configuration of the chiral center common to these two analgesics.

  4. Vocal cord dysfunction during wartime.

    PubMed

    Craig, T; Sitz, K; Squire, E; Smith, L; Carpenter, G

    1992-11-01

    Vocal cord dysfunction (VCD) often masquerades as asthma. The diagnosis is rarely suspected, but should be considered in cases of asthma that present atypically or that fail to respond to standard therapy. The frequency of VCD would be expected to increase during times of stress, including periods of war, since it is thought to be a conversion reaction. A high level of suspicion for VCD is essential to make the diagnosis so as to avoid unnecessary, potentially toxic medications and to direct the patient to prompt psychiatric care, which along with speech therapy, is the cornerstone of care.

  5. Rare Adverse Event Monitoring of Medical Devices with the Use of an Automated Surveillance Tool

    PubMed Central

    Matheny, Michael E.; Arora, Nipun; Ohno-Machado, Lucila; Resnic, Frederic S.

    2007-01-01

    Prospective outcomes surveillance using population level data allows for statistical methodologies and confounder adjustment not supported by the FDA’s current monitoring system. We explored propensity score matching integrated into an automated surveillance tool as a method for confounder adjustment in an observational cohort. The application analyzed all patients undergoing PCI via femoral access route from 2002–2006. The rare outcome of interest was retroperitoneal hemorrhage (RPH) and the device was a vascular closure device (VCD). A propensity score model was developed to match VCD and non-VCD match patients. Our tool was able to detect sustained elevations in RPH among those patients who received a VCD. A root cause analysis revealed an association between high femoral access and RPH which prompted an educational program to modify clinical practice. Our results suggest use of propensity score matching can play a useful role in computer-based surveillance of rare events in a prospective cohort. PMID:18693890

  6. Rare adverse event monitoring of medical devices with the use of an automated surveillance tool.

    PubMed

    Matheny, Michael E; Arora, Nipun; Ohno-Machado, Lucila; Resnic, Frederic S

    2007-10-11

    Prospective outcomes surveillance using population level data allows for statistical methodologies and confounder adjustment not supported by the FDA's current monitoring system. We explored propensity score matching integrated into an automated surveillance tool as a method for confounder adjustment in an observational cohort. The application analyzed all patients undergoing PCI via femoral access route from 2002-2006. The rare outcome of interest was retroperitoneal hemorrhage (RPH) and the device was a vascular closure device (VCD). A propensity score model was developed to match VCD and non-VCD match patients. Our tool was able to detect sustained elevations in RPH among those patients who received a VCD. A root cause analysis revealed an association between high femoral access and RPH which prompted an educational program to modify clinical practice. Our results suggest use of propensity score matching can play a useful role in computer-based surveillance of rare events in a prospective cohort.

  7. 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

    2011-06-09

    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.

  8. Stereochemistry of the tadalafil diastereoisomers: a critical assessment of vibrational circular dichroism, electronic circular dichroism, and optical rotatory dispersion.

    PubMed

    Qiu, Shi; De Gussem, Ewoud; Tehrani, Kourosch Abbaspour; Sergeyev, Sergey; Bultinck, Patrick; Herrebout, Wouter

    2013-11-14

    The stereochemistry of all four stereoisomers of tadalafil is determined using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD) spectroscopy. By comparing experimentally obtained VCD spectra to computationally simulated ones, the absolute configuration of the enantiomeric pair (6R, 12aR)/(6S, 12aS) can be confidently assigned without prior knowledge of their relative stereochemistry. IR and NMR spectra are used to aid the assignment of the relative stereochemistry. The IR and VCD difference spectra further confirm the assignment of all stereoisomers. ECD and ORD spectra are used to investigate the complementarity of the three chiroptical techniques. VCD spectroscopy itself is found to have the ability to identify diastereoisomers, and simultaneous use of these chiroptical spectroscopic methods and NMR chemical shifts aids in increasing the reliability of stereochemistry assignment of diastereoisomers.

  9. 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

  10. Strength by joining methods: combining synthesis with NMR, IR, and vibrational circular dichroism spectroscopy for the determination of the relative configuration in hemicalide.

    PubMed

    De Gussem, Ewoud; Herrebout, Wouter; Specklin, Simon; Meyer, Christophe; Cossy, Janine; Bultinck, Patrick

    2014-12-22

    The relative configuration of a key subunit of hemicalide, a recently isolated, highly bioactive marine natural product having potent antiproliferative activity against a panel of human cancer cell lines, was assigned by combining stereocontrolled synthesis of model substrates with NMR, IR, and vibrational circular dichroism (VCD) spectroscopy. The assignment of the absolute configuration of asymmetric carbon center C42 in two structurally complex epimeric substructures containing six stereocenters by VCD analysis illustrates the power and reliability of combining methods.

  11. Stereochemistry of the Brivaracetam Diastereoisomers.

    PubMed

    Qiu, Shi; Tehrani, Kourosch Abbaspour; Sergeyev, Sergey; Bultinck, Patrick; Herrebout, Wouter; Mathieu, Benoit

    2016-03-01

    The stereochemistry of all four stereoisomers of brivaracetam was determined using vibrational circular dichroism (VCD) spectroscopy. By comparing experimentally obtained VCD spectra and computationally simulated ones, the absolute configurations can be confidently assigned without prior knowledge of their relative stereochemistry. Neither the corrected mean absolute errors analysis of the nuclear magnetic resonance (NMR) data, nor the matching of experimental and calculated infrared spectra allowed the diastereoisomers to be distinguished. VCD spectroscopy itself suffices to establish the absolute configurations of all diastereoisomers. The relative stereochemistry could also be statistically confirmed by matching experimental and computed NMR spectra using the CP3 algorithm. The combination of VCD and NMR is recommended for molecules bearing more than one chiral center, as the relative configurations obtained from NMR serve as an independent check for those established with VCD. Analysis of the calculated VCD spectra reveals that the localized NH2 scissoring mode at around 1600 cm(-1) is characteristic for intramolecular hydrogen bonding, while the orientation of the ethyl group is reflected by the delocalized modes between 1150 and 1050 cm(-1).

  12. Determination of Crosslinking in High Tg Polymers

    DTIC Science & Technology

    1980-07-01

    for Araldite 6004 Cured with Dibutyltin Bis(3-aminopropyl)/hexylamine ...... ................. . 31 5. Duration of Data Collection for Sample T-1...diepoxide [ dibutyltin - bis(3-propylglycidyl ether)]. Bromine containing anhydrides are commercially available in the form of tetrabromophthalic...in three steps: (1) reduction of dibutyltin dichloride to dibutyltin dihydride 3 8 (n-Bu)2SnCl2 + LiAlH4 4 (n-Bu) 2SnH2 (2) hydrostannylation of

  13. Synthesis of Thermally Stable Polymers

    DTIC Science & Technology

    1978-07-01

    LIST OF TABLES Table Page 1 Effect of Catalysts on the Polymerization of Diepoxides and Diisocyanates 11 2 Model Compound Studies 14 3 Polymerization of...Alkynyl-Substituted Polyurethanes 21 6 Effect of Temperature on the Hot Pressing of Polymer 67 24 x SECTION I INTRODUCTION The major objective of this...applying a high-temperature adhesive. Hence, a search for more effective catalysts was carried out. The third approach involved the synthesis of polymers

  14. 1,2,5,6-Diepoxyhexane and 1,2,7,8-diepoxyoctane cross-link duplex DNA at 5'-GNC sequences.

    PubMed

    Yunes, M J; Charnecki, S E; Marden, J J; Millard, J T

    1996-09-01

    The carcinogenicity of epoxide compounds has been attributed to covalent binding to DNA. Whereas monoepoxides form only monoadducts, diepoxides can form both monoadducts and interstrand cross-links. The latter are believed to be the more significant cytotoxic lesions as diepoxides are frequently more carcinogenic and mutagenic than their monoepoxide analogues. We therefore examined the relative DNA interstrand cross-linking capabilities of several diepoxides with respect to chain length, molecular flexibility, reported carcinogenic potential, and DNA sequences targeted. Using denaturing polyacrylamide gel electrophoresis, we found that 1,2,5,6-diepoxyhexane and 1,2,7,8-diepoxyoctane share the 5'-GNC target sequence previously found for 1,2,3,4-diepoxybutane [Millard, J.T., and White, M.M. (1993) Biochemistry 32, 2120-2124] and that the efficiency of cross-linking this sequence may reflect carcinogenicity, 1,2,5,6-Diepoxycyclooctane, the biologically inactive rigid analogue of 1,2,5,6-diepoxyhexane, was found to be a poor cross-linker of all DNA sequences examined. Moreover, increasing the diepoxyalkane chain length did not result in enhanced cross-linking ability.

  15. Vascular Closure Device Failure: Frequency and Implications

    PubMed Central

    Bangalore, Sripal; Arora, Nipun; Resnic, Frederic S.

    2011-01-01

    Background Vascular closure devices (VCDs) are effective at reducing the time to ambulation for patients undergoing cardiac catheterization procedures, and in reducing the risk of vascular complications in selected patient cohorts. However, the frequency and consequence of failure of VCDs is not well defined. Methods and Results From a prospective registry of consecutive patients undergoing cardiac catheterization at our center, 9823 patients who received either a collagen-plug (Angio-Seal®) based or a suture-based (Perclose®) VCD were selected for the study. VCD failure was defined as unsuccessful deployment or failure to achieve hemostasis. Major vascular complication was defined as any retroperitoneal hemorrhage, limb ischemia, or any surgical repair. Minor vascular complication was defined as any groin bleeding, hematoma (≥ 5 cm), pseudoaneurysm or arteriovenous fistula. ‘Any’ vascular complication was defined as either a major or minor vascular complication. Among the 9823 patients in the study, VCD failed in 268 (2.7%; 2.3% diagnostic vs. 3.0% PCI; P = 0.029) patients. Patients with VCD failure had significantly increased risk of any (6.7% vs. 1.4%; P < 0.0001), major (1.9% vs. 0.6%; P = 0.006) or minor (6.0% vs. 1.1%; P < 0.0001) vascular complication compared with the group with successful deployment of VCD. The increased risk of vascular complication was unchanged in a propensity score matched cohort. Conclusions In contemporary practice, VCD failure is rare but when it does fail, it is associated with significant increase in the risk of vascular complications. Patients with VCD failure should be closely monitored to prevent vascular complications. PMID:20031773

  16. 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

  17. Meteorological controls on the vertical distribution of bromine monoxide in the lower troposphere

    NASA Astrophysics Data System (ADS)

    Peterson, P. K.; Simpson, W. R.; Pratt, K. A.; Shepson, P. B.; Frieß, U.; Zielcke, J.; Platt, U.; Walsh, S. J.; Nghiem, S. V.

    2014-09-01

    Multiple axis differential absorption spectroscopy (MAX-DOAS) measurements of bromine monoxide (BrO) probed the vertical structure of halogen activation events during March-May 2012 at Barrow, Alaska. An analysis of the BrO averaging kernels and degrees of freedom obtained by optimal-estimation-based inversions from raw MAX-DOAS measurements reveals the information is best represented by reducing the retrieved BrO profile to two quantities, the integrated column from the surface through 200 m (VCD200 m), and the lower tropospheric vertical column density (LT-VCD) which represents the integrated column of BrO from the surface through 2 km. The percentage of lower-tropospheric BrO in the lowest 200 m was found to be highly variable ranging from shallow layer events, where BrO is present primarily in the lowest 200 m to distributed column events where BrO is observed at higher altitudes. The highest observed LT-VCD events occurred when BrO was distributed throughout the lower troposphere, rather than concentrated near the surface. Atmospheric stability in the lowest 200 m influenced the percentage of LT-VCD that is in the lowest 200 m, with inverted temperature structures having a first-to-third quartile range (Q1-Q3) of VCD200 m/LT-VCD from 15-39% while near neutral temperature structures had a Q1-Q3 range of 7-13%. Data from this campaign show no clear 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 supported the conclusion that the atmospheric stability affects the vertical distribution of BrO.

  18. Dependence of the vertical distribution of bromine monoxide in the lower troposphere on meteorological factors such as wind speed and stability

    NASA Astrophysics Data System (ADS)

    Peterson, P. K.; Simpson, W. R.; Pratt, K. A.; Shepson, P. B.; Frieß, U.; Zielcke, J.; Platt, U.; Walsh, S. J.; Nghiem, S. V.

    2015-02-01

    Multiple axis differential absorption spectroscopy (MAX-DOAS) measurements of bromine monoxide (BrO) probed the vertical structure of halogen activation events during March-May 2012 at Barrow, Alaska. An analysis of the BrO averaging kernels and degrees of freedom obtained by optimal-estimation-based inversions from raw MAX-DOAS measurements reveals the information is best represented by reducing the retrieved BrO profile to two quantities: the integrated column from the surface through 200 m (VCD200 m), and the lower tropospheric vertical column density (LT-VCD), which represents the integrated column of BrO from the surface through 2 km. The percentage of lower tropospheric BrO in the lowest 200 m was found to be highly variable ranging from shallow layer events, where BrO is present primarily in the lowest 200 m, to distributed column events where BrO is observed at higher altitudes. The highest observed LT-VCD events occurred when BrO was distributed throughout the lower troposphere, rather than concentrated near the surface. Atmospheric stability in the lowest 200 m influenced the percentage of LT-VCD that is in the lowest 200 m, with inverted temperature structures having a first-to-third quartile range (Q1-Q3) of VCD200 m/LT-VCD from 15-39%, while near-neutral-temperature structures had a Q1-Q3 range of 7-13%. Data from this campaign show no clear 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 supported the conclusion that the atmospheric stability affects the vertical distribution of BrO.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. A study of aliphatic amino acids using simulated vibrational circular dichroism and Raman optical activity spectra*

    NASA Astrophysics Data System (ADS)

    Ganesan, Aravindhan; Brunger, Michael J.; Wang, Feng

    2013-11-01

    Vibrational optical activity (VOA) spectra, such as vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra, of aliphatic amino acids are simulated using density functional theory (DFT) methods in both gas phase (neutral form) and solution (zwitterionic form), together with their respective infrared (IR) and Raman spectra of the amino acids. The DFT models, which are validated by excellent agreements with the available experimental Raman and ROA spectra of alanine in solution, are employed to study other aliphatic amino acids. The inferred (IR) intensive region (below 2000 cm-1) reveals the signature of alkyl side chains, whereas the Raman intensive region (above 3000 cm-1) contains the information of the functional groups in the amino acids. Furthermore, the chiral carbons of the amino acids (except for glycine) dominate the VCD and ROA spectra in the gas phase, but the methyl group vibrations produce stronger VCD and ROA signals in solution. The C-H related asymmetric vibrations dominate the VOA spectra (i.e., VCD and ROA) > 3000 cm-1 reflecting the side chain structures of the amino acids. Finally the carboxyl and the C(2)H modes of aliphatic amino acids, together with the side chain vibrations, are very active in the VCD/IR and ROA/Raman spectra, which makes such the vibrational spectroscopic methods a very attractive means to study biomolecules.

  4. MAX-DOAS Measurements of Nitrogen Dioxide and Aerosol

    NASA Astrophysics Data System (ADS)

    Mendolia, Deanna

    Multi-axis differential optical absorption spectroscopy (MAX-DOAS) was applied to retrieve tropospheric NO2 and aerosol vertical profiles from downtown Toronto, and King City, Ontario during select periods in 2006 - 2010. Linear regression of MAX-DOAS NO2 vertical column density (VCD) versus OMI (satellite) VCD yielded a good correlation (R = 0.88) and MAX-DOAS negative bias of 20%, which was within the reported uncertainty of the MAX-DOAS and OMI VCD. The average regional Toronto VCD (remotely-sensed via MAX-DOAS and OMI) was half of the near-road VCD obtained in-situ (2.4 x 1016 ± 1.2 x 1016 molec/cm2 ). MAX-DOAS measurements of O4 were coupled with radiative transfer modeling to obtain vertical aerosol extinction profiles and aerosol optical depth (AOD). A strong linear agreement was observed between PM 2.5 concentration and aerosol extinction coefficient (R = 0.92), and MAX-DOAS versus sun photometer AOD (slope = 0.94; R= 0.90).

  5. On chirality transfer in electron donor-acceptor complexes. A prediction for the sulfinimine···BF3 system.

    PubMed

    Rode, Joanna E; Dobrowolski, Jan Cz

    2012-01-01

    Stabilization energies of the electron donor-acceptor sulfinimine···BF(3) complexes calculated at either the B3LYP/aug-cc-pVTZ or the MP2/aug-cc-pVTZ level do not allow to judge, whether the N- or O-atom in sulfinimine is stronger electron-donor to BF(3) . The problem seems to be solvable because chirality transfer phenomenon between chiral sulfinimine and achiral BF(3) is expected to be vibrational circular dichroism (VCD) active. Moreover, the bands associated with the achiral BF(3) molecule are predicted to be the most intense in the entire spectrum. However, the VCD band robustness analyses show that most of the chirality transfer modes of BF(3) are unreliable. Conversely, variation of VCD intensity with change of intermolecular distance, angle, and selected dihedrals between the complex partners shows that to establish the robustness of chirality transfer mode. It is also necessary to determine the influence of the potential energy surface (PES) shape on the VCD intensity. At the moment, there is still no universal criterion for the chirality transfer mode robustness and the conclusions formulated based on one system cannot be directly transferred even to a quite similar one. However, it is certain that more attention should be focused on relation of PES shape and the VCD mode robustness problem.

  6. Determination of Molecular Structure of Bisphenylene Homologues of BINOL-Based Phosphoramidites by Chiroptical Methods

    NASA Astrophysics Data System (ADS)

    Julínek, Ondřej; Setnička, Vladimír; Miklášová, Natalia; Putala, Martin; Ruud, Kenneth; Urbanová, Marie

    2009-09-01

    Vibrational (VCD), electronic circular dichroism (ECD), and IR absorption spectra together with transparent spectral region optical rotation (OR) of two derivatives of bisphenylene 1,1'-binaphthyl-based phosphoramidites containing three stereogenic axes were measured and the results were compared with simulated data obtained by ab initio calculations with density functional theory. An excellent agreement between experimental and predicted B3LYP/6-31G** and BPW91/6-31G** VCD spectra enabled the assignment of all VCD bands in the experimental spectra, while the Gibbs free energy of all the conformers allowed the determination of their relative populations. The calculation of ECD spectra showed that CAM-B3LYP/6-311G** provided results superior to those of B3LYP/6-311G**. The theoretical results for the OR at the B3LYP/6-311G** and CAM-B3LYP/6-311G** levels were in good agreement with experimental optical rotations, but exhibited lower sensitivity in determining particular conformers than VCD and ECD. By a careful comparison of experimental VCD, IR, and ECD spectra and OR with calculated data, it was possible to assign the absolute configuration of all three stereogenic axes and to determine the molecular structure of the studied bisphenylene 1,1'-binaphthyl-based phosphoramidites in solution with a high degree of confidence.

  7. Effects of electron configuration and coordination number on the vibrational circular dichroism spectra of metal complexes of trans-1,2-diaminocyclohexane.

    PubMed

    Merten, Christian; Hiller, Kaitlynd; Xu, Yunjie

    2012-10-05

    Transition metal complexes of ethylenediamine have attracted significant interest as prototype systems for a range of studies related to their chiroptical properties. In order to better elucidate the effects of different central metal ions and also different coordination numbers on the vibrational circular dichroism (VCD) spectra, trans-1,2-diamino cyclohexane (chxn) was chosen as the chiral ligands in the current report. In this case the conformation of the diamino ligand is predetermined by its absolute configuration and the transition from the λ- to the δ-form that can occur in the case of ethylenediamine is no longer possible. The fingerprint region of the vibrational absorption and VCD spectra of three transition metal complexes of chxn have been analysed in detail. For the tris chelate complexes Ni(chxn)(3)(2+) and Cu(chxn)(3)(2+), selective enhancement of some VCD bands in the otherwise almost identical spectra has been observed and explained in terms of a ring current mechanism and of a different number of unpaired electrons of the metal centers. The comparison of the VCD spectra of Cu(chxn)(3)(2+) and Cu(chxn)(2)(2+) reveals the effects of coordination number that manifest as an inversion of the strong bisignate VCD pattern of the NH(2) scissor vibrational modes. This leads to the conclusion that this region can be used to extract information about the ligand environment and the chirality of the metal center.

  8. [Vocal cord dysfunction. An important differential diagnosis to bronchial asthma].

    PubMed

    Kothe, C; Schade, G; Fleischer, S; Hess, M

    2004-03-01

    Vocal cord dysfunction (VCD) is described as a functional disorder of the vocal folds which leads to an intermittent, inspiratory 'paradoxical' glottal closure. We report on three women with frequent repetitive shortness of breath attacks caused by VCD. This was diagnosed by transnasal videofiberendoscopy, with glottal closure being seen during inspiration. Because of the different etiologies, one of the patients was treated with breathing and speech therapy, another received Omeprazol for laryngopharyngeal reflux, and the third was treated by intralaryngeal botulinum toxin injections. All three patients showed a reduction in attacks. Clinically, VCD seems to mimic asthma. However, with a thorough patient history and diagnostics, especially with transnasal laryngoscopy during a (triggered) attack, a precise diagnosis seems possible.

  9. The sensitivity analysis in the nitrogen dioxide retrieval from space borne measurement

    NASA Astrophysics Data System (ADS)

    Zhang, Ying; Chen, Fu L.; Han, Dong; Yu, Chao; Tao, Hua J.; Su, Lin

    2014-11-01

    In this paper, we demonstrated the best fitting window and spectral resolution to retrieve NO2 Vertical Column Density (VCD) from space borne spectrometer in ultra-violet. The reflectance at TOA was simulated with atmospheric radiation transfer model SCIATRAN, which takes both molecules absorption and aerosol multiple scattering into consideration. The NO2 VCD was retrieved using the Differential Optical Absorption Spectroscopy (DOAS) method. There are five kinds of factors has been taken into the NO2 VCD retrieval sensitivity analysis: fitting window and spectral resolution, aerosol optical thickness, surface albedo, NO2 concentration in the lower troposphere and sun-satellite geometry. The results showed that DOAS method cannot well filter the aerosol scattering. High surface reflectivity can strengthen the signal at TOA and thus enhance the retrieval accuracy. The AMFs become larger dramatically when the sun or satellite zenith angels are above 70 degree, while the relative azimuth angel affects little in the AMF.

  10. 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.

  11. 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

  12. Determination of absolute configuration of chiral molecules using vibrational optical activity: a review.

    PubMed

    He, Yanan; Wang, Bo; Dukor, Rina K; Nafie, Laurence A

    2011-07-01

    Determination of the absolute handedness, known as absolute configuration (AC), of chiral molecules is an important step in any field related to chirality, especially in the pharmaceutical industry. Vibrational optical activity (VOA) has become a powerful tool for the determination of the AC of chiral molecules in the solution state after nearly forty years of evolution. VOA offers a novel alternative, or supplement, to X-ray crystallography, permitting AC determinations on neat liquid, oil, and solution samples without the need to grow single crystals of the pure chiral sample molecules as required for X-ray analysis. By comparing the sign and intensity of the measured VOA spectrum with the corresponding ab initio density functional theory (DFT) calculated VOA spectrum of a chosen configuration, one can unambiguously assign the AC of a chiral molecule. Comparing measured VOA spectra with calculated VOA spectra of all the conformers can also provide solution-state conformational populations. VOA consists of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA). Currently, VCD is used routinely by researchers in a variety of backgrounds, including molecular chirality, asymmetric synthesis, chiral catalysis, drug screening, pharmacology, and natural products. Although the application of ROA in AC determination lags behind that of VCD, with the recent implementation of ROA subroutines in commercial quantum chemistry software, ROA will in the future complement VCD for AC determination. In this review, the basic principles of the application of VCD to the determination of absolute configuration in chiral molecules are described. The steps required for VCD spectral measurement and calculation are outlined, followed by brief descriptions of recently published papers reporting the determination of AC in small organic, pharmaceutical, and natural product molecules.

  13. Regional modeling of tropospheric NO2 vertical column density over East Asia during the period 2000-2010: comparison with multisatellite observations

    NASA Astrophysics Data System (ADS)

    Itahashi, S.; Uno, I.; Irie, H.; Kurokawa, J.-I.; Ohara, T.

    2014-04-01

    Satellite observations of the tropospheric NO2 vertical column density (VCD) are closely correlated to, and thus can be used to estimate, surface NOx emissions. In this study, the NO2 VCD simulated by a regional chemical transport model with emissions data from the updated Regional Emission inventory in ASia (REAS) version 2.1 were validated through comparison with multisatellite observations during the period 2000-2010. Rapid growth in NO2 VCD (~11% year-1) driven by the expansion of anthropogenic NOx emissions was identified above the central eastern China (CEC) region, except for the period during the economic downturn. In contrast, slightly decreasing trends (~2% year-1) were identified above Japan accompanied by a decline in anthropogenic emissions. To systematically compare the modeled NO2 VCD, we estimated sampling bias and the effect of applying the averaging kernel information, with particular focus on the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) data. Using the updated REAS, the modeled NO2 VCD reasonably reproduced annual trends observed by multisatellites, suggesting that the rate of increase of NOx emissions estimated by the updated REAS inventory would be robust. Province-scale revision of emissions above CEC is needed to further refine emission inventories. Based on the close linear relationship between modeled and observed NO2 VCD and anthropogenic NOx emissions, NOx emissions in 2009 and 2010, which were not covered by the updated REAS inventory, were estimated. NOx emissions from anthropogenic sources in China in 2009 and 2010 were determined to be 26.4 and 28.5 Tg year-1, respectively, indicating that NOx emissions increased more than twofold between 2000 and 2010. This increase reflected the strong growth of anthropogenic emissions in China following the rapid recovery from the economic downturn from late 2008 until mid-2009. Our method consists of simple estimations from satellite observations and

  14. 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

  15. Chiroptical studies on supramolecular chirality of molecular aggregates.

    PubMed

    Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

    2015-10-01

    The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates.

  16. Vibrational circular dichroism spectra for large molecules and molecules with heavy elements.

    PubMed

    Reiter, Kevin; Kühn, Michael; Weigend, Florian

    2017-02-07

    We present an implementation of vibrational circular dichroism (VCD) spectra in TURBOMOLE. We mainly followed the route proposed by Cheeseman [Chem. Phys. Lett. 252, 211 (1996)] and extended the modules for calculating the magnetic response and vibrational frequencies accordingly. The implementation allows for gauge origin invariant employment of effective core potentials, as demonstrated for Co(ppy)3, ppy = 2-Phenylpyridine. In this way, scalar relativistic effects are covered and heavy elements can be treated. Further, with the present implementation molecular symmetry may be efficiently exploited, which makes the calculation of large (symmetric) systems feasible. The calculation of the VCD spectrum of icosahedral C620(2+) is shown as an illustrative application.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Vibrational circular dichroism spectra for large molecules and molecules with heavy elements

    NASA Astrophysics Data System (ADS)

    Reiter, Kevin; Kühn, Michael; Weigend, Florian

    2017-02-01

    We present an implementation of vibrational circular dichroism (VCD) spectra in TURBOMOLE. We mainly followed the route proposed by Cheeseman [Chem. Phys. Lett. 252, 211 (1996)] and extended the modules for calculating the magnetic response and vibrational frequencies accordingly. The implementation allows for gauge origin invariant employment of effective core potentials, as demonstrated for Co(ppy)3, ppy = 2-Phenylpyridine. In this way, scalar relativistic effects are covered and heavy elements can be treated. Further, with the present implementation molecular symmetry may be efficiently exploited, which makes the calculation of large (symmetric) systems feasible. The calculation of the VCD spectrum of icosahedral C6202+ is shown as an illustrative application.

  2. Absolute Configuration Determination by Quantum Mechanical Calculation of Chiroptical Spectra: Basics and Applications to Fungal Metabolites.

    PubMed

    Superchi, Stefano; Scafato, Patrizia; Górecki, Marcin; Pescitelli, Gennaro

    2017-03-10

    The application of quantum mechanical simulation of chiroptical properties, i.e. electronic circular dichroism (ECD), optical rotation (OR), and vibrational circular dichroism (VCD), to the assignment of the absolute configuration of chiral naturally occurring metabolites of fungal origin, is reviewed. The fundamentals of such chiroptical spectroscopies as well as the specific experimental and computational issues allied to the application of their ab initio calculation is reported. Some examples, related to the use of the ECD, VCD, and OR techniques and highlighting the practical application of the methods, are also described.

  3. (2R*,4R*,7S*,10R*,12R*)-3,11,13,15-Tetra-oxa-penta-cyclo-[5.5.3.0(1,7).0(2,4).0(10,12)]penta-deca-5,8-dien-14-one.

    PubMed

    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 mol-ecules 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 C(δ+)=O(δ-) dipoles of neighbouring carbonate moieties.

  4. Diastereoselective synthesis of 2,3,4,5,6-pentafluoroheptanes.

    PubMed

    Farran, Daniel; Slawin, Alexandra M Z; Kirsch, Peer; O'Hagan, David

    2009-09-18

    A stereocontrolled synthesis of alkanes containing five contiguous fluorine atoms is presented. The compounds were prepared by sequential fluorination of diastereoisomeric alcohol-diepoxides. The chemistry involved epoxide ring-opening with HF.NEt(3) and deshydroxyfluorination reactions of free alcohols with Deoxo-Fluor. The fluorination reactions were all highly stereospecific, with all five fluorines being incorporated in three sequential steps. Three different diastereoisomers of the 2,3,4,5,6-pentafluoroheptyl motif were prepared as heptane-1,7-diol derivatives, a structural format amenable for incorporation of the vicinal pentafluoro scaffold into larger molecular architectures.

  5. 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 %)

  6. 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

  7. 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.

  8. Nucleic acid vibrational circular dichroism, absorption, and linear dichroism spectra. I. A DeVoe theory approach.

    PubMed Central

    Self, B D; Moore, D S

    1997-01-01

    Infrared (IR) vibrational circular dichroism (VCD), absorption, and linear dichroism (LD) spectra of four homopolyribonucleotides, poly(rA), poly(rG), poly(rC), and poly(rU), have been calculated, in the 1750-1550 cm-1 spectral region, using the DeVoe polarizability theory. A newly derived algorithm, which approximates the Hilbert transform of imaginaries to reals, was used in the calculations to obtain real parts of oscillator polarizabilities associated with each normal mode. The calculated spectra of the polynucleotides were compared with previously measured solution spectra. The good agreement between calculated and measured polynucleotide spectra indicates, for the first time, that the DeVoe theory is a useful means of calculating the VCD and IR absorption spectra of polynucleotides. For the first time, calculated DeVoe theory VCD and IR absorption spectra of oriented polynucleotides are presented. The calculated VCD spectra for the oriented polynucleotides are used to predict the spectra for such measurements made in the future. The calculated IR spectra for the oriented polynucleotides are useful in interpreting the linear dichroism of the polynucleotides. PMID:9199798

  9. Ultrasonographic features of vascular closure devices: initial and 6-month follow-up results

    PubMed Central

    2014-01-01

    Purpose: This study aimed to evaluate the ultrasonographic findings for various types of vascular closure devices (VCDs) immediately after the angiographic procedure and at 6-month follow-up. Methods: We included 18 VCDs including Angio-Seal (n=4), FemoSeal (n=8), ExoSeal (n=3), Perclose (n=2), and StarClose (n=1) in this study. Four patients were implanted with 2 VCDs at the each side of bilateral femoral arteries, while the remaining 8 patients were inserted 1 VCD at the right femoral artery. Ultrasonography was performed within 10 days and at approximately 6 months after the angiographic procedure. Ultrasonographic morphology of the attached VCD and its relationship with the arterial wall were analyzed. Results: Initial ultrasonography revealed the attached VCD as the relevant unique structure with successful deployment and hemostasis. Follow-up ultrasonography demonstrated partial absorption of hemostatic materials in cases of Angio-Seal (n=3), FemoSeal (n=5), and ExoSeal (n=3), changes in the soft tissue surrounding the femoral artery in case of Angio-Seal (n=1), arterial intimal hyperplasia in cases of FemoSeal (n=3), and no gross changes as compared with the initial ultrasonographic findings in cases of Perclose (n=2) and StarClose (n=1). Conclusion: Initial ultrasonographic evaluation reflected the unique structure of each VCD, with most of them being easily distinguishable. Follow-up ultrasonography revealed various changes in the affected vessels. PMID:25145584

  10. New chiral cyclooctatriene-based polycyclic architectures.

    PubMed

    Pieters, Grégory; Gaucher, Anne; Marrot, Jérôme; Maurel, François; Naubron, Jean-Valère; Jean, Marion; Vanthuyne, Nicolas; Crassous, Jeanne; Prim, Damien

    2011-08-19

    The synthesis and properties of new chiral polycyclic architectures that display both helicity and a saddle-type shape are described. The enantiomers have been separated, and their absolute configuration was determined by VCD and ECD. The unprecedented molecular architecture is based on a cyclooctatriene core surrounded by an association of benzo[c]fluorene and ortho-phenylene units.

  11. Command and Control Research and Technology Symposium (2004):The Power Age Concepts and Technologies. Improving Tactical PSYOP Video Dissemination in Media-Austere Operating Environments

    DTIC Science & Technology

    2007-11-02

    the production and dissemination of all PSYOP products prepared on videocassettes, Digital Video Disc (DVD) or video compact-disc ( VCD ) computer...Pashtun, the 9-11 attacks and America’s response.75 At first, the 82d Airborne Division TPTs showed the video, prepared on DVDs and VCDs , on laptop

  12. 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.

  13. Fitting Technology to the Mathematics Pedagogy: Its Effect on Students' Academic Achievement

    ERIC Educational Resources Information Center

    Gano, Leila R.

    2011-01-01

    Taking advantage of student's passion in using technology in the form of digital media sets the trend of this study. If this passion can be harnessed, digital media may have an important and powerful role to play in education. A methodology of teaching using digital media in the form of VCD is experimented and tested for possible effect on…

  14. The Perceived Role of ICTs in Quality of Life in Three Chinese Cities

    ERIC Educational Resources Information Center

    Lee, Paul S. N.; Leung, Louis; Lo, Venhwei; Xiong, Chengyu

    2008-01-01

    This study assesses the perceived role of information and communication technologies (ICTs) including the Internet, mobile telephone, CD/MD/MP3, television and VCR/VCD/DVD in raising quality of life (QoL). A comparison is made between three Chinese cities, namely, Beijing, Taipei and Hong Kong, to see if differences exist in the perceived value of…

  15. Vibrational Optical Activity of BODIPY Dimers: The Role of Magnetic-Electric Coupling in Vibrational Excitons.

    PubMed

    Abbate, Sergio; Bruhn, Torsten; Pescitelli, Gennaro; Longhi, Giovanna

    2017-01-12

    The vibrational exciton (VE) interpretation of intense bisignated couplets in vibrational circular dichroism (VCD) spectra of a pair of atropisomeric BODIPY (boron dipyrrin) dimers is discussed. The role of intrinsic magnetic moments is crucial to reproduce the different behaviors of quasi-isomeric BODIPY dimers with different aryl junction.

  16. Nonplanar tertiary amides in rigid chiral tricyclic dilactams. Peptide group distortions and vibrational optical activity.

    PubMed

    Pazderková, Markéta; Profant, Václav; Hodačová, Jana; Sebestík, Jaroslav; Pazderka, Tomáš; Novotná, Pavlína; Urbanová, Marie; Safařík, Martin; Buděšínský, Miloš; Tichý, Miloš; Bednárová, Lucie; Baumruk, Vladimír; Maloň, Petr

    2013-08-22

    We investigate amide nonplanarity in vibrational optical activity (VOA) spectra of tricyclic spirodilactams 5,8-diazatricyclo[6,3,0,0(1,5)]undecan-4,9-dione (I) and its 6,6',7,7'-tetradeuterio derivative (II). These rigid molecules constrain amide groups to nonplanar geometries with twisted pyramidal arrangements of bonds to amide nitrogen atoms. We have collected a full range vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra including signals of C-H and C-D stretching vibrations. We report normal-mode analysis and a comparison of calculated to experimental VCD and ROA. The data provide band-to-band assignment and offer a possibility to evaluate roles of constrained nonplanar tertiary amide groups and rigid chiral skeletons. Nonplanarity shows as single-signed VCD and ROA amide I signals, prevailing the couplets expected to arise from the amide-amide interaction. Amide-amide coupling dominates amide II (mainly C'-N stretching, modified in tertiary amides by the absence of a N-H bond) transitions (strong couplet in VCD, no significant ROA) probably due to the close proximity of amide nitrogen atoms. At lower wavenumbers, ROA spectra exhibit another likely manifestation of amide nonplanarity, showing signals of amide V (δ(oop)(N-C) at ~570 cm(-1)) and amide VI (δ(oop)(C'═O) at ~700 cm(-1) and ~650 cm(-1)) vibrations.

  17. 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.

  18. Chromatographic and spectroscopic studies on the chiral recognition of sulfated beta-cyclodextrin as chiral mobile phase additive enantiomeric separation of a chiral amine.

    PubMed

    Ma, Shengli; Shen, Sherry; Haddad, Nizar; Tang, Wenjun; Wang, Jing; Lee, Heewon; Yee, Nathan; Senanayake, Chris; Grinberg, Nelu

    2009-02-20

    A fast enantiomeric separation of a chiral aromatic amine was achieved, using ultra high pressure liquid chromatography and highly sulfated beta-cyclodextrin (S-beta-CD) as a chiral additive in the mobile phase. The stationary phase consisted of a core-shell support with a particle size of 2.7mum. Under these conditions the base-line separation was obtained within 2.5min. The influence of the concentration of the additive, along with the thermodynamics of the separation, was studied. Vibrational circular dichroism (VCD) spectroscopy was applied to assess the absolute configuration of the two enantiomeric analytes, as well as the interaction of these enantiomers with the S-beta-CD. The VCD results revealed that S-beta-CD undergoes a temperature-induced conformational change. Further, VCD experiments indicate that the interactions of the two enantiomers with the S-beta-CD occur through an inclusion of the aromatic part of the analyte, as well as through electrostatic interaction between the protonated amine and the sulfate groups located at the narrow part of the S-beta-CD. Molecular mechanics calculations performed according to the VCD results are consistent with experimental data, providing further evidence of these interactions.

  19. Patient Satisfaction After Femoral Arterial Access Site Closure Using the ExoSeal{sup ®} Vascular Closure Device Compared to Manual Compression: A Prospective Intra-individual Comparative Study

    SciTech Connect

    Pieper, Claus Christian Thomas, Daniel; Nadal, Jennifer; Willinek, Winfried A. Schild, Hans Heinz Meyer, Carsten

    2016-01-15

    PurposeTo intra-individually compare discomfort levels and patient satisfaction after arterial access closure using the ExoSeal{sup ®} vascular closure device (VCD) and manual compression (MC) in a prospective study design.MethodsPatients undergoing two planned interventions from 07/2013 to 09/2014 could participate in the study. Access closure was performed with an ExoSeal{sup ®}-VCD in one and MC in the other intervention. Patients were clinically and sonographically examined and were given questionnaires 1 day after intervention [groin- and back-pain during bedrest (100-point visual analog scale; 0: no pain); comfortability of bedrest (10-point Likert scale, 1: comfortable), satisfaction with closure (10-point Likert scale, 1: very satisfied)]. Results were analyzed in a cross-over design.Results48 patients (29 male, median age 62.5 (32–88) years) were included. An ExoSeal{sup ®}-VCD was used first in 25 cases. As four of these subsequently refused MC as second intervention, data from 44 patients could be analyzed. All closures were technically successful (successful device deployment) without major complications. Groin- and back-pain after VCD-use/MC was 0 (0–15) vs. 10 (0–80) and 0 (0–75) vs. 25 (0–90), respectively (p < 0.0001). Bedrest after VCD-use was more comfortable than after MC [1 (range 1–7) vs. 6 (2–10); p < 0.0001]. Satisfaction with the closure procedure and with the intervention in general was higher after VCD-use compared to MC [1 (1–3) vs. 5 (2–10) and 1 (1–2) vs. 2 (1–4), respectively; p < 0.0001].ConclusionIntra-individual comparison showed pain levels and discomfort to be significantly lower after ExoSeal{sup ®} use compared to MC. VCD closure was associated with higher satisfaction both with the closure itself and with the intervention in general.

  20. 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

  1. A chronic reference value for 1,3-butadiene based on an updated noncancer toxicity assessment.

    PubMed

    Grant, Roberta L; Haney, Joseph; Curry, Angela L; Honeycutt, Michael

    2010-08-01

    A chronic noncancer toxicity assessment for 1,3-butadiene (BD) has been conducted by the Texas Commission on Environmental Quality (TCEQ) using information not available to the U.S. Environmental Protection Agency (U.S. EPA) in 2002. The TCEQ developed a chronic reference value (ReV) of 33 microg/m3 (15 ppb). The chronic ReV is based on the same animal study and critical endpoint used by U.S. EPA for ovarian atrophy in B6C3F1 mice, but uses mode of action (MOA) information that indicates the diepoxide metabolite is responsible for ovarian atrophy. In addition, diepoxide-specific hemoglobin adduct data in mice, rats, and humans and other experimental data that became available after 2002 were used to support a conservative data-derived toxicokinetic animal-to-human uncertainty factor (UFA) of 0.3. The default toxicodynamic UFA of 3 was used, together with the data-derived toxicokinetic UFA of 0.3, resulting in a total UFA of 1. The necessary experimental data were not available to calculate a chemical-specific adjustment factor, although supporting data suggest the toxicokinetic UFA may range from 0.01 to 0.2. The chronic ReV value, along with a unit risk factor developed by the TCEQ, will be used to evaluate ambient air monitoring data so that the general public is protected against adverse health effects from chronic exposure to BD.

  2. 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).

  3. 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.

  4. 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.

  5. A Systematic Review of Psychological Interventions for Adult and Pediatric Patients with Vocal Cord Dysfunction

    PubMed Central

    Guglani, Loveleen; Atkinson, Sarah; Hosanagar, Avinash; Guglani, Lokesh

    2014-01-01

    Background: Vocal cord dysfunction (VCD) or paradoxical vocal-fold motion (PVFM) is a functional disorder of the vocal cords that requires multidisciplinary treatment. Besides relaxation techniques, the use of psychological interventions can help treat the underlying psychological co-morbidities. There is currently no literature that examines the effectiveness of psychological interventions for VCD/PVFM. Objectives: To review the evidence for psychological interventions used for the treatment of patients with VCD/PVFM. Data sources: We searched electronic databases for English medical literature using Pubmed (Medline), PsycInfo, Cochrane Database of Systematic Reviews, Cochrane Central Registry of Controlled Trials, and Clinicaltrials.gov. The date range for our search is from June 1964 to June 2014. Study eligibility criteria, participants, and interventions: We included studies that reported the use of psychological interventions in both adults and children diagnosed with VCD/PVFM. We included randomized controlled trials, case-control studies, retrospective chart reviews, prospective case series, and individual case reports. Results: Most reported studies are small case series or individual case reports that have described the use of interventions such as psychotherapy, behavioral therapy, use of anti-anxiety and anti-depressant medications, and hypnotherapy in conjunction with breathing exercises taught by speech therapists for symptomatic relief. Among the various psychological interventions that have been reported, there is no data regarding effectiveness and/or superiority of one approach over another in either adult or pediatric patients. Conclusions: Psychological interventions have a role to play in the management of adult and pediatric patients with VCD/PVFM. Future prospective studies using uniform approaches for treatment of associated psychopathology may help address this question. PMID:25152871

  6. Simulated IR, isotropic and anisotropic Raman, and vibrational circular dichroism amide I band profiles of stacked β-sheets.

    PubMed

    Schweitzer-Stenner, Reinhard

    2012-04-12

    The amide I mode is a highly structure sensitive vibration of polypeptides that gives rise to a very strong band in IR absorption and a moderate band in Raman spectra. Many theoretical simulations of IR-band profiles have been undertaken thus far in order to expand the usability of amide I for the structure analysis of peptides and proteins. These simulations have thus far focused on the IR band profiles and to a limited extent on calculating the corresponding vibrational circular dichroism (VCD) signal. In this paper, we use excitonic coupling theory to simulate the IR, isotropic Raman, anisotropic Raman, and VCD band profiles of amide I of parallel and antiparallel β-sheets as well as of two layers of stacked β-sheets with antiparallel and parallel orientations of the respective sheets. Our calculations reveal anisotropic Raman and to a lesser extent VCD amide I profiles rather than the corresponding IR profile as suitable tools to discriminate between parallel and antiparallel β-sheets. Stacking has a very limited influence on the Raman and IR band profiles, but enhance the VCD signal, the sign of which allows one to discriminate between parallel and antiparallel orientations of stacked sheets. Helical twisting and bending of parallel β-sheets give rise to a very enhanced positive couplet, in agreement with the recent work of Schweitzer-Stenner and Measey (J. Am. Chem. Soc., 2011, 133, 1066). Stochastic uncorrelated inhomogeneity of individual peptide groups causes significant asymmetric broadening of Raman bands and, to a lesser extent, of IR bands and reduces the VCD-couplet of stacked β-sheets.

  7. Vibrational circular dichroism in general anisotropic thin solid films: measurement and theoretical approach.

    PubMed

    Buffeteau, Thierry; Lagugné-Labarthet, François; Sourisseau, Claude

    2005-06-01

    In this study, the measurement of the true vibrational circular dichroism (VCD) spectrum is considered from an experimental and theoretical approach for any general anisotropic thin solid sample exhibiting linear as well as circular birefringence (LB, CB) and dichroism (LD, CD) properties. For this purpose, we have made use of a simple model alpha-helix polypeptide, namely, the poly(gamma-benzyl-L-glutamate) or PBLG, reference sample possessing a well-known VCD spectrum and giving rise to slightly oriented films by deposition onto a solid substrate. Also, we have used a different Fourier transform infrared modulation of polarization (PM-FTIR) optical setup with two-channel electronic processing in order to record the PM-VLD and PM-VCD spectra for various sample orientations in its film plane. All the corresponding general relations of the expected intensities in these experiments and the related properly designed calibration measurements were established using the Stokes-Mueller formalism; in addition, the residual birefringence of the optical setup and the transmittance anisotropy of the detector were estimated. From a comparative study of the results obtained in solution and in the solid state, we then propose a simple new experimental procedure to extract the true VCD spectrum of an oriented PBLG thin film: its consists of calculating the half-sum of two spectra recorded at theta and at theta +/- 90 degrees sample orientations. Moreover, the complete linear and circular birefringence and dichroism properties of the ordered PBLG thin film are estimated in the amide I and amide II vibrational regions. This allows us to establish for any sample orientation various theoretical simulations of the VCD spectra that agree nicely with the observed experimental results; this confirms that the measurement of LD and LB is in this case a prerequisite in simulating the true VCD spectrum of a partly oriented anisotropic sample. This validates our combined experimental and

  8. 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

  9. 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.

  10. Thermolysis of (1R,2R)-1,2-dideuteriocyclobutane. An application of vibrational circular dichroism to kinetic analysis

    SciTech Connect

    Chickos, J.S.; Annamalai, A.; Keiderling, T.A.

    1986-07-23

    The relative rates of geometric isomerization to racemization have been studied for the title compound by using a combination of infrared (IR) and vibrational circular dichroism (VCD) spectroscopies, respectively. The results are interpreted with a kinetic and mechanistic scheme which parallels that used by Berson, Pedersen, and Carpenter on a similar study of chiral cyclopropane-d/sub 2/ thermolysis. Relative rates of isomerization to stereomutation of 1.5 +/- 0.4 were obtained which can be interpreted to be consistent with a mechanism best described by random methylene rotation in tetramethylene-d/sub 2/. This is the first application of VCD to kinetic analysis, and the advantages of IR techniques over the more usually employed UV spectroscopies to this type of basic mechanistic problem are illustrated.

  11. [Gastroesophageal reflux as a cause of vocal dysfunction].

    PubMed

    Young, P; Finn, B C; Fox, M L; Emery, N; Bruetman, J E

    2008-07-01

    Vocal cord dysfunction (VCD), is characterized by a paradoxical adduction of the vocal cords during inspiration, and occurs predominantly in young women. Common symptoms are cough, wheezing, episodic dyspnea, and inspiratory stridor. The true incidence and course of the disease are unknown, and it is usually self limited. It can coexist with, or mimic refractory asthma. Psychological disorders were thought to be the principal cause, subsequently multiple organic diseases have also been reported, like gastroesophageal reflux disease (GERD). Diagnosis is made by clinical suspicion and direct observation. The Gold standard for diagnosis is laryngoscopy with visualization of the paradoxical motion of the vocal cords when the patient is symptomatic. Speech therapy and psychotherapy have been used extensively without any prospective study. We report two cases of VCD associated with GERD, both with excellent respond to treatment.

  12. Helical Inversion of Gel Fibrils by Elongation of Perfluoroalkyl Chains as Studied by Vibrational Circular Dichroism.

    PubMed

    Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

    2016-05-01

    Vibrational circular dichroism (VCD) spectroscopy was applied to gelation by a chiral low-molecular mass weight gelator, N,N'-diperfluoroalkanoyl-1,2-trans-diaminocyclohexane. Attention was focused on the winding effects of (-CF2 )n chains on the gelating ability. For this purpose, a series of gelators were synthesized with perfluoroalkyl chains of different length (n = 6-8). When gelation was studied using acetonitrile as a solvent, the fibrils took different morphologies, depending on the chain length: twisted saddle-like ribbon or helical ribbon from fibril (n = 6) and a helical ribbon from platelet (n = 8). The signs of VCD peaks assigned to the couplet of C=O stretching and to the C-F stretching were also dependent on n, indicating that a gelator molecule changed conformation on elongating perfluoroalkyl chains. A model is proposed for the aggregation modes in fibrils. Chirality 28:361-364, 2016. © 2016 Wiley Periodicals, Inc.

  13. 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.

  14. Point Defects in Pb-, Bi-, and In-Doped CdZnTe Detectors: Deep-Level Transient Spectroscopy (DLTS) Measurements

    NASA Astrophysics Data System (ADS)

    Gul, R.; Keeter, K.; Rodriguez, R.; Bolotnikov, A. E.; Hossain, A.; Camarda, G. S.; Kim, K. H.; Yang, G.; Cui, Y.; Carcelen, V.; Franc, J.; Li, Z.; James, R. B.

    2012-03-01

    We studied, by current deep-level transient spectroscopy (I-DLTS), point defects induced in CdZnTe detectors by three dopants: Pb, Bi, and In. Pb-doped CdZnTe detectors have a new acceptor trap at around 0.48 eV. The absence of a VCd trap suggests that all Cd vacancies are compensated by Pb interstitials after they form a deep-acceptor complex [[PbCd]+-V{Cd/2-}]-. Bi-doped CdZnTe detectors had two distinct traps: a shallow trap at around 36 meV and a deep donor trap at around 0.82 eV. In detectors doped with In, we noted three well-known traps: two acceptor levels at around 0.18 eV (A-centers) and 0.31 eV (VCd), and a deep trap at around 1.1 eV.

  15. A vibrational circular dichroism approach to the determination of the absolute configurations of flavorous 5-substituted-2(5H)-furanones.

    PubMed

    Nakahashi, Atsufumi; Yaguchi, Yoshihiro; Miura, Nobuaki; Emura, Makoto; Monde, Kenji

    2011-04-25

    Sotolon (1) and maple furanone (2) are naturally occurring chiral furanones. These 5-substituted-2(5H)-furanones are industrially significant aroma compounds due to their characteristic organoleptic properties and extraordinarily low odor thresholds. Each enantiomer of 1 and 2 was successfully obtained by preparative enantioselective supercritical fluid chromatography. The absolute configuration of 1 was confirmed as (R)-(-)-1 and (S)-(+)-1 by adopting the vibrational circular dichroism (VCD) approach. The absolute configuration of 2, which has remained ambiguous since its discovery in 1957, was determined as (R)-(+)-2 and (S)-(-)-2 for the first time by the VCD technique. Surprisingly, the signs of the optical rotation of 2 are opposite of those of 1 regardless of their identical absolute configurations. This observation emphasizes the risk in absolute configurational assignments based on comparison of optical rotation signs of similar structures. Odor evaluation of the enantiomers of 2 revealed different odor intensities.

  16. INFRARED AND RAMAN VIBRATIONAL OPTICAL ACTIVITY: Theoretical and Experimental Aspects

    NASA Astrophysics Data System (ADS)

    Nafie, Laurence A.

    1997-10-01

    Advances in the field of vibrational optical activity (VOA) are reviewed over the past decade. Topics are surveyed with an emphasis on the theoretical and instrumental progress in both vibrational circular dichroism (VCD) and Raman optical activity (ROA). Applications of VOA to stereochemical and biological problems are reviewed, with a bias toward new kinds of experiments made possible by theoretical and instrumental advances. In the field of VCD, the most notable advances have taken place in the quality and size of ab initio calculations of VOA intensities and in the quality of step-scan Fourier transform instrumentation. For ROA, the most dramatic progress has occurred in the areas of theoretical formulation and high-throughput instrumentation. Applications of VOA now include all major classes of biological and pharmaceutical molecules. VOA's importance as a diagnostic tool will likely grow as the control of molecular chirality increases in research and industrial areas.

  17. Conformational change of a chiral Schiff base Ni(II) complex with a binaphthyl moiety: application of vibrational circular dichroism spectroscopy.

    PubMed

    Sato, Hisako; Mori, Yukie; Yamagishi, Akihiko

    2013-05-21

    Vibrational circular dichroism (VCD) spectroscopy was applied to study the structural change of a Ni(II) complex (denoted by [Ni(II)L]) with a chiral Schiff base ligand, (R)- or (S)-2,2'-bis(salicylideneamino)-1,1'-binaphthyl (denoted by H2L), in solution. The major signals in the mid-IR region were assigned on the basis of comparison with the DFT-calculated spectra. The complex transformed reversibly between the square-planar, tetrahedral and octahedral configurations, depending on solvents and temperature. The observed changes in the VCD peaks accompanying the transformation were analyzed in terms of the conformational change of the chiral ligand with a focus on the twisting angle in the Schiff base backbone and the dihedral angle of the binaphthyl group.

  18. 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.

  19. 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.

  20. A Ka-band reflection-type analog electrically controlled phase shifter

    NASA Astrophysics Data System (ADS)

    Li, Wenchao; Chen, Yanhui; Shen, Hui; Zhang, Bin

    2017-03-01

    In order to modulate the phase of RF signal continuously, a new miniaturized Ka-band analog electrically controlled phase shifter is presented. The phase shifter based on 90°directional coupler and parallel variable capacitance diodes(VCD) achieves matching circuit and shift phase, the circuit can gain wide range phase shift by changing the bias voltage of variable capacitance diodes (VCD), and the insertion loss fluctuations of the phase shifter has a significant improvement by parallel compensation resistance. Simulation and experimental results show that the phase shifter in 29˜31 GHz range obtains 180° phase shift, the insertion loss is better than 6.5 dB, and the insertion loss fluctuations are within 1 dB.

  1. Detailed structural study of β-artemether: Density functional theory (DFT) calculations of Infrared, Raman spectroscopy, and vibrational circular dichroism

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiang; Chen, Jianchao; Li, Linwei; Zhou, Zhixu; Geng, Yiding; Sun, Tiemin

    2015-10-01

    In this study, the experimental and theoretical studies on the structure of β-artemether are presented. The optimized molecular structure, Mulliken atomic charges, vibrational spectra (IR, Raman and vibrational circular dichroism), and molecular electrostatic potential have been calculated by density functional theory (DFT) using B3LYP method with the 6-311++G (2d, p) basis set. Reliable vibrational assignments for Artemether have been made on the basis of potential energy distribution (PED). The vibrational circular dichroism (VCD) has been explored by ab initio calculations, and then was used to compare with the experimental VCD. The consistence between them confirmed the absolute configuration of Artemether. In addition, HOMO-LUMO of the title compound as well as thermo-dynamical parameters has illustrated the stability of β-artemether.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

  3. Late onset iatrogenic limb ischaemia after deployment of an Angio-Seal vascular closure device.

    PubMed

    Krishna, Rama K; Kherada, Nisharahmed; Beohar, Nirat

    2015-04-26

    It is common practice to deploy a vascular closure device for access site closure after percutaneous angiography or cardiovascular interventions for immediate haemostasis and to facilitate early discharge. We encountered two octogenarian women who underwent and had subsequent vascular access site closure with Angio-Seal (St Jude) and who later presented with limb ischaemia needing surgical revascularisation. Our patients had undergone uneventful deployment of the Angio-Seal vascular closure device (VCD) at the right common femoral artery (CFA) access site with successful haemostasis. About 3 weeks later they presented with features of limb ischaemia needing further diagnostic work-up including repeat angiography, which revealed subtotal occlusion of right common femoral artery at the level of prior access and Angio-Seal deployment site. Both the patients underwent successful surgical repair with restoration of distal flow and resolution of symptoms. These cases illustrate the late presentation of VCD-related complications with limb ischaemia, needing surgical revascularisation.

  4. 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

  5. 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.

  6. A Test Fixture for Simulating Human Limb Physiology and Soft Tissue Biomechanics

    DTIC Science & Technology

    1989-04-14

    int, int); vodse p~rocess-di sp(vcd)3void d,-cwLoop-outline(void); "T~ eor disclosure of report data is subject to the restriction on the Title 27...setstclr( &briQ• htgr •, &bright green); s1:ext• ecstbL ); setstctr( &li3•_blue, &kigh•, blue ); i det [cur,’); ) el,•e if (gl grlh• == 2 !! Q1_gr• == 3) ( l•s

  7. Electronic and vibrational circular dichroism spectra of (R)-(-)-apomorphine

    NASA Astrophysics Data System (ADS)

    Abbate, Sergio; Longhi, Giovanna; Lebon, France; Tommasini, Matteo

    2012-09-01

    Apomorphine is a chiral drug molecule; notwithstanding its extraordinary importance, little attention has been paid to the characterization of its chiroptical properties. Here we report on its electronic circular dichroism (ECD) spectra, recorded in methanol and water, and vibrational circular dichroism (VCD) in methanol and dimethyl sulfoxide (DMSO) solutions. Density functional theory (DFT) calculations have allowed us to interpret the spectra and to evaluate the role of possible conformations, charge-states and interactions with counter ions.

  8. 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.

  9. Development Of Optically-Addressed Liquid Crystal Spatial Light Modulators (OA SLM) Operating In Reflective Mode With Diameter 50 Mm Using A-Si:C:H Photoconductors And Nematic And Ferroelectric Liquid Crystals

    DTIC Science & Technology

    2005-10-17

    of the illumination intensity starts to grow again. This effect is observed for the definite range of feeding voltage frequencies. There was... irradiation of photoconductor (PC) layer the voltage, applied to it, grows in just 1-2 V. This variation of the voltage is comparable with the contact...Hence, one can provide the control over the voltage – current dependence (VCD) of irradiated PC in the range of small voltages by means of directed

  10. 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.

  11. Characterization of the synthetic cannabinoid MDMB-CHMCZCA

    PubMed Central

    Schollmeyer, Dieter; Münster-Müller, Sascha

    2016-01-01

    The synthetic cannabinoid MDMB-CHMCZCA was characterized by various spectroscopic techniques including NMR spectroscopy and tandem mass spectrometry. The synthetic sample was found to be of S-configuration by VCD spectroscopy and comparison of the data with DFT calculations, while ECD spectroscopy was found to be inconclusive in this case. The enantiomeric purity of samples from test purchases and police seizures was assessed by a self-developed chiral HPLC method. PMID:28144353

  12. Balancing Mission Requirement for Networked Autonomous Rotorcrafts Performing Video Reconnaissance

    DTIC Science & Technology

    2009-08-01

    velocity vcd (t) as⎡⎣ vxhdvyhd vzhd ⎤⎦ = ⎡⎣ 1 0 00 cos θ − sin θ 0 sin θ cos θ ⎤⎦⎡⎣ vxcdvycd vzcd ⎤⎦ (13) ⎡⎣ ωxhdωyhd ωzhd ⎤⎦ = ⎡⎣ 1 0 00 cos θ − sin θ 0 sin

  13. Starclose SE® hemostasis after 6F direct antegrade superficial femoral artery access distal to the femoral head for peripheral endovascular procedures in obese patients

    PubMed Central

    Spiliopoulos, Stavros; Kitrou, Panagiotis; Christeas, Nikolaos; Karnabatidis, Dimitris

    2016-01-01

    PURPOSE Direct superficial femoral artery (SFA) antegrade puncture is a valid alternative to common femoral artery (CFA) access for peripheral vascular interventions. Data investigating vascular closure device (VCD) hemostasis of distant SFA 6F access are limited. We aimed to investigate the safety and effectiveness of the Starclose SE® VCD for hemostasis, following direct 6F antegrade SFA access distal to the femoral head. METHODS This prospective, single-center study included patients who were not suitable for CFA puncture and were scheduled to undergo peripheral endovascular interventions using direct antegrade SFA 6F access, at least 2 cm below the inferior edge of femoral head. Hemostasis was obtained with the Starclose SE® VCD (Abbott Laboratories). Primary endpoints were successful hemostasis rate and periprocedural (30-day) major complication rate. Secondary endpoint was the rate of minor complications. Clinical and Doppler ultrasound follow-up was performed at discharge and at one month. RESULTS Between September 2014 and August 2015, a total of 30 patients (21 male; 70.0%) with a mean body mass index of 41.2 kg/m2 were enrolled. Mean age was 72±9 years (range, 67–88 years). Most patients suffered from critical limb ischemia (87.1%) and diabetes (61.3%). Calcifications were present in eight cases (26.6%). Reason for direct SFA puncture was obesity (100%). Successful hemostasis was achieved in 100% of the cases. No major complications were noted after one-month follow-up. Minor complications included two <5 cm hematomas (6.6%) not necessitating treatment. CONCLUSION In this prospective study, Starclose SE® VCD was safe and effective for hemostasis of antegrade direct SFA puncture. Uncomplicated hemostasis was achieved even in cases of puncturing 2 to 7 cm below the inferior edge of the femoral head. PMID:27641942

  14. 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.

  15. Synthesis, reactivity and application studies for different biolubricants.

    PubMed

    Salimon, Jumat; Abdullah, Bashar Mudhaffar; Yusop, Rahimi M; Salih, Nadia

    2014-03-10

    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.

  16. Biological effects of DNA damage in the hyperthermophilic archaeon Sulfolobus acidocaldarius.

    PubMed

    Reilly, Michelle S; Grogan, Dennis W

    2002-02-19

    To investigate the generality of efficient double-strand break repair and damage-induced mutagenesis in hyperthermophilic archaea, we systematically measured the effects of five DNA-damaging agents on Sulfolobus acidocaldarius and compared the results to those obtained for Escherichia coli under corresponding conditions. The observed lethality of gamma-radiation was very similar for S. acidocaldarius and E. coli, arguing against unusually efficient double-strand break repair in S. acidocaldarius. In addition, DNA-strand-breaking agents (gamma-radiation or bleomycin), as well as DNA-cross-linking agents (mechlorethamine, butadiene diepoxide or cisplatin) stimulated forward mutation, reverse mutation, and formation of recombinants via conjugation in Sulfolobus cells. Although two of the five DNA-damaging agents failed to revert the E. coli auxotrophs under these conditions, all five reverted S. acidocaldarius auxotrophs.

  17. 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

  18. Comparison of the capacity fade of Sony US 18650 cells charged with different protocols

    NASA Astrophysics Data System (ADS)

    Sikha, G.; Ramadass, P.; Haran, B. S.; White, R. E.; Popov, Branko N.

    A new varying current decay (VCD) protocol, which charges the Li-ion battery at a faster rate, was developed. The performance of the battery charged using the VCD protocol was compared with the performance of batteries charged with conventional constant current-constant voltage (CC-CV) and constant voltage (CV) protocols. The destructive physical analysis tests at the end of 150 cycles indicated higher impedance for the cells cycled using the VCD protocol compared to the cell charged using the conventional (CC-CV) mode. The observed increase of the impedance was due to a small increase of the potential above the cut-off value of 4.2 for short times. A complete capacity fade material balance as a function of number of cycles was performed in order to account for the total capacity loss due to different charging protocols used. The loss of primary active material (Li +), the secondary active material (LiCoO 2/carbon) and the rate capability losses were determined for Sony US 18650 Li-ion cells and compared for different charging protocols.

  19. Circular dichroism spectroscopy study of crystalline-to-amorphous transformation in chiral platinum(II) complexes.

    PubMed

    Zhang, Xiao-Peng; Wu, Tao; Liu, Jian; Zhao, Jin-Cheng; Li, Cheng-Hui; You, Xiao-Zeng

    2013-07-01

    Two couples of enantiomeric platinum(II) complexes: Pt(L1a )Cl (1a), Pt(L1b )Cl (1b) and Pt(L1a )(C ≡ C - Ph) (2a), Pt(L1b )(C ≡ C - Ph) (2b) (L1a  = (+)-1,3-di-(2-(4,5-pinene)pyridyl)benzene, L1b  = (-)-1,3-di-(2-(4,5-pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X-ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline-to-amorphous transformation. The crystalline solids, grinding-induced amorphous powders, and vapor-induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid-state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra.

  20. Risk predictors of retroperitoneal hemorrhage following percutaneous coronary intervention.

    PubMed

    Tiroch, Klaus A; Arora, Nipun; Matheny, Michael E; Liu, Christopher; Lee, Timothy C; Resnic, Frederic S

    2008-12-01

    Retroperitoneal hemorrhage (RPH) is a potentially catastrophic complication after percutaneous coronary intervention (PCI). Previous studies identified female gender, body surface area, and high arterial puncture location as independent risk factors for RPH. There have been conflicting reports regarding the association with vascular closure devices (VCDs). Chronic renal insufficiency (CRI) and diabetes mellitus have been associated with both peripheral vascular disease and vascular access-site complications. The putative association of VCDs, CRI, and diabetes mellitus with RPH in the contemporary PCI era was investigated. A total of 3,062 consecutive patients undergoing 3,482 PCIs at Brigham and Women's Hospital from January 2005 to April 2007 were evaluated for the study. All 3,311 patients with femoral angiography underwent hand-caliper-based quantitative vascular analysis and were included in this analysis. Multivariate analysis was performed using a backwards selection algorithm, and a propensity adjustment was developed to control for possible confounding variables regarding VCD use. The incidence of RPH was 0.49% (17 of 3,482 patients). After multivariate and propensity analyses, covariates that significantly influenced the risk of RPH were CRI, glycoprotein IIb/IIIa inhibitors, and high arterial puncture (p < or =0.007). VCD use was not independently associated with the development of RPH (p = 0.74). In conclusion, this large prospective cohort study identified CRI, but not VCD use, as an independent predictor for RPH and peripheral vascular disease.

  1. Rehabilitation of the cavernous smooth muscle in patients with organic erectile dysfunction.

    PubMed

    Salem, H; Mostafa, T

    2012-04-01

    This study aimed at assessing the effect of regular use of intracorporeal injection (ICI), sildenafil citrate and vacuum constriction device (VCD) on cavernous smooth muscle and erectile activity. One hundred and sixty-five patients with organic erectile dysfunction were investigated for 3 months. The patient and his partner were classified prospectively after proper counselling: group I (n = 56) received ICI twice per week; group II (n = 55) received sildenafil 100 mg twice per week; and group III (n = 54) used VCD twice per week. Duplex ultrasound was carried out before and after treatment, and then, the patients were followed up for a month to assess the resumption of unaided erection. The results showed that there was significant improvement in mean peak systolic velocity (PSV) and mean cavernosal artery diameter (CAD) at the end of the treatment in all groups, being higher in the ICI group than in the other two groups. Also, the percentage of patients who resumed unaided intercourse were higher in the ICI group compared with the other two groups (17.9%, 9.1% and 3.7% respectively). It is concluded that repeated regular use of ICI, sildenafil or VCD by patients with organic erectile dysfunction has a positive impact on their cavernous blood flow and erectile activity.

  2. CD44: A Multifunctional Cell Surface Adhesion Receptor Is a Regulator of Progression and Metastasis of Cancer Cells

    PubMed Central

    Senbanjo, Linda T.; Chellaiah, Meenakshi A.

    2017-01-01

    CD44 is a cell surface adhesion receptor that is highly expressed in many cancers and regulates metastasis via recruitment of CD44 to the cell surface. Its interaction with appropriate extracellular matrix ligands promotes the migration and invasion processes involved in metastases. It was originally identified as a receptor for hyaluronan or hyaluronic acid and later to several other ligands including, osteopontin (OPN), collagens, and matrix metalloproteinases. CD44 has also been identified as a marker for stem cells of several types. Beside standard CD44 (sCD44), variant (vCD44) isoforms of CD44 have been shown to be created by alternate splicing of the mRNA in several cancer. Addition of new exons into the extracellular domain near the transmembrane of sCD44 increases the tendency for expressing larger size vCD44 isoforms. Expression of certain vCD44 isoforms was linked with progression and metastasis of cancer cells as well as patient prognosis. The expression of CD44 isoforms can be correlated with tumor subtypes and be a marker of cancer stem cells. CD44 cleavage, shedding, and elevated levels of soluble CD44 in the serum of patients is a marker of tumor burden and metastasis in several cancers including colon and gastric cancer. Recent observations have shown that CD44 intracellular domain (CD44-ICD) is related to the metastatic potential of breast cancer cells. However, the underlying mechanisms need further elucidation. PMID:28326306

  3. Determination of the absolute configurations at stereogenic centers in the presence of axial chirality.

    PubMed

    Polavarapu, Prasad L; Jeirath, Neha; Kurtán, Tibor; Pescitelli, Gennaro; Krohn, Karsten

    2009-01-01

    Cephalochromin, a homodimeric naphthpyranone natural product, contains both axial chirality due to the hindered rotation along the biaryl axis and central chirality due to the C-2, C-2' stereogenic centers of the fused pyranone ring. For determining the absolute configurations (ACs) of central chirality elements, different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotation (OR), have been used. From these experimental data, in conjunction with corresponding quantum chemical predictions at B3LYP/6-311G* level, it is found that the ECD spectra of cephalochromin are dominated by its axial chirality and are not suitable to distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers and hence to determine the ACs of the central chirality elements. OR signs also did not distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers. On other hand, VCD spectrum of cephalochromin exhibited separate spectral features attributable to axial chirality and stereogenic centers, thereby allowing the determination of both types of chirality elements. This is the first investigation demonstrating that, because of vibrations specific to the studied stereogenic centers, VCD spectroscopy can be used to simultaneously determine the ACs of axial and central chirality elements whenever other chiroptical methods (ECD and OR) fail to report on them.

  4. First principles study of O defects in CdSe

    NASA Astrophysics Data System (ADS)

    T-Thienprasert, J.; Limpijumnong, S.; Du, M.-H.; Singh, D. J.

    2012-08-01

    Recently, the vibrational signatures related to oxygen defects in oxygen-doped CdSe were measured using ultrahigh resolution Fourier transform infrared (FTIR) spectroscopy by Chen et al.(2008) [1]. They observed two absorption bands centered at ∼1991.77 and 2001.3 cm-1, which they attributed to the LVMs of OCd, in the samples grown with the addition of CdO and excess Se. For the samples claimed to be grown with even more excess Se, three high-frequency modes (1094.11, 1107.45, and 1126.33) were observed and assigned to the LVMs of OSe-VCd complex. In this work, we explicitly calculated the vibrational signatures of OCd and OSe-VCd complex defects based on first principles approach. The calculated vibrational frequencies of OCd and OSe-VCd complex are inconsistent with the frequencies observed by Chen et al., indicating that their observed frequencies are from other defects. Potential defects that could explain the experimentally observed modes are suggested.

  5. Water vapor retrieval from OMI visible spectra

    NASA Astrophysics Data System (ADS)

    Wang, H.; Liu, X.; Chance, K.; González Abad, G.; Miller, C. Chan

    2014-06-01

    There are distinct spectral features of water vapor in the wavelength range covered by the Ozone Monitoring Instrument (OMI) visible channel. Although these features are much weaker than those at longer wavelengths, they can be exploited to retrieve useful information about water vapor. They have an advantage in that their small optical depth leads to fairly simple interpretation as measurements of the total water vapor column density. We have used the Smithsonian Astrophysical Observatory (SAO) OMI operational retrieval algorithm to derive the slant column density (SCD) of water vapor using the 430-480 nm spectral region after extensive optimization. We convert from SCD to vertical column density (VCD) using the air mass factor (AMF), which is calculated using look-up tables of scattering weights and assimilated water vapor profiles. Our Level 2 product includes not only water vapor VCD but also the associated scattering weights and AMF. In the tropics, our standard water vapor product has a median SCD of 1.3 × 1023 molecules cm-2 and a median relative uncertainty of about 11%, about a factor of 2 better than that from a similar OMI algorithm that uses a narrower retrieval window. The corresponding median VCD is about 1.2 × 1023 molecules cm-2. We have examined the sensitivities of SCD and AMF to various parameters and compared our results with those from the GlobVapour product, the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Aerosol Robotic NETwork (AERONET).

  6. Dimethyl Sulfoxide Induced Destabilization and Disassembly of Various Structural Variants of Insulin Fibrils Monitored by Vibrational Circular Dichroism.

    PubMed

    Zhang, Ge; Babenko, Viktoria; Dzwolak, Wojciech; Keiderling, Timothy A

    2015-12-15

    Dimethyl sulfoxide (DMSO) induced destabilization of insulin fibrils has been previously studied by Fourier transform infrared spectroscopy and interpreted in terms of secondary structural changes. The variation of this process for fibrils with different types of higher-order morphological structures remained unclear. Here, we utilize vibrational circular dichroism (VCD), which has been reported to provide a useful biophysical probe of the supramolecular chirality of amyloid fibrils, to characterize changes in the macroscopic chirality following DMSO-induced disassembly for two types of insulin fibrils formed under different conditions, at different reduced pH values with and without added salt and agitation. We confirm that very high concentrations of DMSO can disaggregate both types of insulin fibrils, which initially maintained a β-sheet conformation and eventually changed their secondary structure to a disordered form. The two types responded to varying concentrations of DMSO, and disaggregation followed different mechanisms. Interconversion of specific insulin fibril morphological types also occurred during the destabilization process as monitored by VCD. With transmission electron microscopy, we were able to correlate the changes in VCD sign patterns to alteration of morphology of the insulin fibrils.

  7. 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

  8. 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

  9. 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

  10. Comparison of engraftment following different stem cell mobilization modalities in patients with multiple myeloma treated with a uniform induction regimen containing bortezomib, cyclophosphamide and dexamethasone.

    PubMed

    Benyamini, Noam; Avivi, Irit; Dann, Eldad J; Zuckerman, Tsila; Lavi, Noa; Katz, Tami

    2017-03-01

    Bortezomib-based induction followed by autologous stem cell transplantation is a common treatment for multiple myeloma (MM). Stem cell (SC) mobilization with granulocyte-colony stimulating factor (G-CSF) alone has become an alternative to G-CSF combined with chemotherapeutic agents. This study aimed to compare the efficacy of the two mobilization modalities following induction with a uniform regimen containing bortezomib, cyclophosphamide and dexamethasone (VCD). We retrospectively evaluated results of SC mobilization using either G-CSF alone or combined with high-dose cyclophosphamide (HD-CY) in MM patients after VCD induction. The primary endpoints of the study were engraftment and mobilization-associated toxicity. Parameters of stem cell collection, transplantation and engraftment were assessed. Data of 92 patients were analyzed [56 (61%) mobilized with HD-CY + G-CSF and 36 (39%) with G-CSF only]. HD-CY + G-CSF provided a higher number of CD34 + cells (15.9 vs 8.1 × 10(6)/kg, p = 0.001) with fewer apheresis sessions. However, while no adverse events were observed in patients receiving G-CSF alone, nine patients (16%) receiving HD-CY + G-CSF developed neutropenic fever requiring hospitalization. Although a greater number of cells was transplanted following mobilization with HD-CY + G-CSF, neutrophil and platelet engraftment and duration of transplant-related hospitalization were similar in both cohorts. G-CSF alone provided a sufficient SC amount, without exposing patients to additional toxicity. While HD-CY + G-CSF resulted in a superior SC yield in MM patients induced with VCD, this advantage should be balanced against adverse effects of this mobilization regimen.

  11. The DELTA Network Study of Distributed Automated Post-Market Cardiovascular Device Safety Surveillance

    PubMed Central

    Kumar, Amit; Matheny, Michael E.; Ho, Kalon K.L.; Yeh, Robert W.; Piemonte, Thomas C.; Waldman, Howard; Shah, Pinak B.; Cope, Richard; Normand, Sharon-Lise; Donnelly, Sharon; Robbins, Susan; Resnic, Frederic S.

    2016-01-01

    Background Current approaches for post-market medical device safety surveillance are limited in their ability to produce timely and accurate assessments of adverse event rates. Methods and Results The DELTA (Data Extraction and Longitudinal Trend Analysis) network study was a multicenter prospective observational study designed to evaluate the safety of devices used during percutaneous coronary interventions (PCI). All adult patients undergoing PCI from January 2008 through December 2012 at five participating Massachusetts sites were included. A safety alert was triggered if the cumulative observed adverse event rates for the study device exceeded the upper 95% confidence interval of the event rates of propensity-matched control cohort. Pre-specified sensitivity analyses were developed to validate any identified safety signal. A total of 23,805 consecutive PCI procedures were evaluated. Two out of 24 safety analyses triggered safety alerts. Patients receiving Perclose vascular closure device (VCD) experienced an increased risk of minor vascular complications (relative risk [RR] 4.14; p <0.01) and any vascular complication (RR: 2.06; p = 0.01) as compared with propensity-matched patients receiving alternative VCD; a result primarily driven by relatively high event rates at one participating center. Sensitivity analyses based on alternative risk adjustment methods confirmed the a pattern of increased rate of complications at one of the five participating sites in their use of Perclose VCD. Conclusions The DELTA network study demonstrates that distributed automated prospective safety surveillance has the potential of providing near real-time assessment of safety risks of newly approved medical devices. PMID:25491915

  12. 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.

    2003-12-01

    Nitrogen oxides (NO+NO2=NOx and reservoir species) 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 a 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. By estimating and subtracting the stratospheric column, and considering radiative transfer, vertical column densities (VCD) of tropospheric NO2 can be determined (e.g. Leue et al., 2001). 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 may help to identify the different anthropogenic source categories. Furthermore, we estimated the lifetime of tropospheric NO2 by analysing the mean weekly cycle exemplarily over Germany, obtaining a value of about 6 h in summer and 18-24 h in winter.

  13. 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.

  14. Rapid methods for inversion of MAXDOAS elevation profiles to surface-associated box concentrations, visibility, and heights: application to analysis of Arctic BrO events

    NASA Astrophysics Data System (ADS)

    Donohoue, D.; Carlson, D.; Simpson, W. R.

    2010-11-01

    Multiple Axis Differential Optical Absorption Spectroscopy (MAXDOAS) is a remote sensing technique that measures surface-associated trace gas profiles using simple automated instrumentation that requires very low power and is deployable at remote sites. However, the analysis of MAXDOAS data is complex and often cannot be applied rapidly or consistently over long measurement periods. Here we present three transparent methods to analyze MAXDOAS data. The box profile method finds the best trace gas layer height and surface-associated vertical column density (VCD) to simultaneously fit oxygen collisional dimer (O4) and trace gas differential slant column density (dSCD) observations. The elevated viewing method estimates the surface-associated VCD from observations at high view elevations, such as 10° and 20°. The horizon viewing method estimates the surface concentration of a trace gas by using near-horizon view trace gas and O4 data. We apply these methods to a two-month data set and show that the methods retrieve information 80% of the time and provides a consistent time series. Surface-associated trace gas VCD observations by the elevated viewing method correlate (r2 > 0.93) with the box profile method with slopes within 15% of unity. Surface-associated concentration observations from the horizon viewing method correlate well (r2 > 0.90) with the box profile method and a slope within 4% of unity. Application of these retrieval methods to UV-absorbing trace gases other than BrO is straightforward, and application in other spectral regions is discussed. These methods provide rapid and comprehensive inversions of MAXDOAS spectral data that are useful during field campaigns, as well as, verification of more complex (e.g. optimal estimate inversion) methods.

  15. Ground based MAX-DOAS measurements of the total water vapor column and comparison with model results and satellite observations

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Mies, K.; Beirle, S.

    2012-04-01

    Multi-AXis- (MAX-) DOAS instruments observe scattered sun light under different, mostly slant elevation angles. From such measurements the tropospheric profile or column density of many atmospheric trace gases like e.g. NO2 or HCHO can be derived. Here we analyse the total atmospheric column density of water vapor from MAX-DOAS measurements made at Mainz, Germany in 2011. We performed measurements in the red spectral range, where water vapor shows some very characteristic and strong absorption features. The determination of the atmospheric water vapor column density (the so called vertical column density, VCD) is performed in three steps: first the slant column density of H2O is analysed from the measured spectra of scattered sun light. Second, a correction for the saturation of the H2O absorption is performed, which arises from the fact that the narrow H2O absorption lines are not resolved by our instrument. Third, the geometric approximation is applied to deterine the H2O VCD from the retrieved H2O slant column densities. In contrast to observations at shorter wavelengths, the application of the geometric approximation should lead to smaller errors because of the much weaker Rayleigh-scattering by air moilecules in the red spectral range. Also the effects of clouds are expected to be relatively mall, at least for mid and high level clouds. Information on the cloud properties can be derived from the simultaneously measured absorption of the oxygen molecule (O2) and oxygen dimer (O4). We compare our MAX-DOAS H2O VCD to indepenent data sets like satellite observations and model simulations.

  16. 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.

  17. 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

    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

  18. Measurements of tropospheric NO2 column at a rural site southwest of Beijing using Mini-MAX-DOAS instruments

    NASA Astrophysics Data System (ADS)

    Jin, Junli; Ma, Jianzhong; Shaiganfar, Reza; Wagner, Thomas

    2014-05-01

    Tropospheric vertical column density (VCD) of NO2 retrieved from satellite observations has been widely used in atmospheric chemistry research in China. An underestimation of tropospheric NO2 has been found for satellite with respect to passive DOAS ground measurement in megacities, e.g., Beijing and Shanghai. Therefore, MAX-DOAS ground measurements in the non-urban sites are specially needed to validate the satellite data for a wide area in China. The Gucheng site (39 deg 08 min N, 115 deg 40 min E, 15.2 m asl) is located in the polluted rural area of North China, with a distant about 110km southwest of Beijing, 130 km west of Tianjin, and 160 km northeast of Shijiazhuang. We performed ground-based MAX-DOAS measurements in Gucheng from 1 September 2008 through 30 September 2010. The two year's DOAS spectra data are analyzed with a focus on tropospheric NO2 at the first stage. Here we present the results of the retrieved tropospheric NO2 VCDs at this site, including the diurnal, weekly and seasonal variations and cloud effects. We find a prominent seasonal variation pattern of tropospheric NO2 VCD over Guocheng, with a monthly mean minimum occurring during summertime and a monthly mean maximum in wintertime. We also find two peaks in the tropospheric NO2 VCD diurnal variations in spring, autumn and winter, occurring around 8:00 BJT and 17:00 BJT respectively. These retrieved results will be used to validate satellite products of tropospheric NO2 VCDs.

  19. Ag(I)-mediated homo and hetero pairs of guanosine and cytidine: Monitoring by circular dichroism spectroscopy

    NASA Astrophysics Data System (ADS)

    Goncharova, Iryna

    2014-01-01

    Ag(I)-containing compounds are attractive as antibacterial and antifungal agents. The renewed interest in the application of silver(I) compounds has led to the need for detailed knowledge of the mechanism of their action. One of the possible ways is the coordination of Ag(I) to G-C pairs of DNA, where Ag+ ions form Ag(I)-mediated base pairs and inhibit the transcription. Herein, a systematic chiroptical study on silver(I)-mediated homo and mixed pairs of the C-G complementary-base derivatives cytidine(C) and 5‧-guanosine monophosphate(G) in water is presented. Ag(I)-mediated homo and hetero pairs of G and C and their self-assembled species were studied under two pH levels (7.0 and 10.0) by vibrational (VCD) and electronic circular dichroism(ECD). VCD was used for the first time in this field and showed itself to be a powerful method for obtaining specific structural information in solution. Based on results of the VCD experiments, the different geometries of the homo pairs were proposed under pH 7.0 and 10.0. ECD was used as a diagnostic tool to characterize the studied systems and as a contact point between the previously defined structures of the metal or proton mediated pairs of nucleobases and the systems studied here. On the basis of the obtained data, the formation of the self-assembled species of cytidine with a structure similar to the i-motif structure in DNA was proposed at pH 10.0.

  20. 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

  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. 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).

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Comparison of the electronic and vibrational optical activity of a europium(III) complex.

    PubMed

    Wu, Tao; Hudecová, Jana; You, Xiao-Zeng; Urbanová, Marie; Bouř, Petr

    2015-04-07

    The geometry and the electronic structure of chiral lanthanide(III) complexes are traditionally probed by electronic methods, such as circularly polarised luminescence (CPL) and electronic circular dichroism (ECD) spectroscopy. The vibrational phenomena are much weaker. In the present study, however, significant enhancements of vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectral intensities were observed during the formation of a chiral bipyridine-Eu(III) complex. The ten-fold enhancement of the vibrational absorption and VCD intensities was explained by a charge-transfer process and the dominant effect of the nitrate ion on the spectra. A much larger enhancement of the ROA and Raman intensities and a hundred-fold increase of the circular intensity difference (CID) ratio were explained by the resonance of the λ = 532 nm laser light with the (7)F0 → (5)D0 transitions. This phenomenon is combined with a chirality transfer, and mixing of the Raman and luminescence effects involving low-energy (7)F states of europium. The results thus indicate that the vibrational optical activity (VOA) may be a very sensitive tool for chirality detection and probing of the electronic structure of Eu(III) and other coordination compounds.

  12. Applications of the Cartesian coordinate tensor transfer technique in the simulations of vibrational circular dichroism spectra of oligonucleotides.

    PubMed

    Andrushchenko, Valery; Bouř, Petr

    2010-01-01

    The application of the Cartesian coordinate tensor transfer (CCT) technique for simulations of the IR absorption and vibrational circular dichroism (VCD) spectra of relatively large nucleic acid fragments is demonstrated on several case studies. The approach is based on direct ab initio calculations of atomic tensors, determining molecular properties, for relatively small fragments, and subsequent transfer of these tensors to the larger systems in Cartesian coordinates. This procedure enables precise computations of vibrational spectra for large biomolecular systems, currently with up to several thousands of atoms. The versatile ability of the CCT methods is emphasized on the examples of VCD and IR absorption spectra calculations for B- and Z-forms of DNA, single-, double-, and triple-stranded RNA helices and DNA structures with different base content and sequences. The development and recent improvements of the methodology are followed, including utilization of the constrained normal mode optimization (NMO) strategy and combined quantum mechanics and molecular dynamics simulations. Advantages, drawbacks, and recommendations for future improvements of the CCT method as applied to nucleic acid spectra calculations are discussed.

  13. Chirality and chiroptical properties of amyloid fibrils.

    PubMed

    Dzwolak, Wojciech

    2014-09-01

    Chirality of amyloid fibrils-linear beta-sheet-rich aggregates of misfolded protein chains-often manifests in morphological traits such as helical twist visible in atomic force microscopy and in chiroptical properties accessible to vibrational circular dichroism (VCD). According to recent studies the relationship between molecular chirality of polypeptide building blocks and superstructural chirality of amyloid fibrils may be more intricate and less deterministic than previously assumed. Several puzzling experimental findings have put into question earlier intuitive ideas on: 1) the bottom-up chirality transfer upon amyloidogenic self-assembly, and 2) the structural origins of chiroptical properties of protein aggregates. For example, removal of a single amino acid residue from an amyloidogenic all-L peptide was shown to reverse handedness of fibrils. On the other hand, certain types of amyloid aggregates revealed surprisingly strong VCD spectra with the sign and shape dependent on the conditions of fibrillation. Hence, microscopic and chiroptical studies have highlighted chirality as one more aspect of polymorphism of amyloid fibrils. This brief review is intended to outline the current state of research on amyloid-like fibrils from the perspective of their structural and superstructural chirality and chiroptical properties.

  14. 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.

  15. 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.

  16. Some exact tests for manifest properties of latent trait models

    PubMed Central

    De Gooijer, Jan G.; Yuan, Ao

    2011-01-01

    Item response theory is one of the modern test theories with applications in educational and psychological testing. Recent developments made it possible to characterize some desired properties in terms of a collection of manifest ones, so that hypothesis tests on these traits can, in principle, be performed. But the existing test methodology is based on asymptotic approximation, which is impractical in most applications since the required sample sizes are often unrealistically huge. To overcome this problem, a class of tests is proposed for making exact statistical inference about four manifest properties: covariances given the sum are non-positive (CSN), manifest monotonicity (MM), conditional association (CA), and vanishing conditional dependence (VCD). One major advantage is that these exact tests do not require large sample sizes. As a result, tests for CSN and MM can be routinely performed in empirical studies. For testing CA and VCD, the exact methods are still impractical in most applications, due to the unusually large number of parameters to be tested. However, exact methods are still derived for them as an exploration toward practicality. Some numerical examples with applications of the exact tests for CSN and MM are provided. PMID:21562625

  17. The cerebellum and cognition: cerebellar lesions do not impair spatial working memory or visual associative learning in monkeys.

    PubMed

    Nixon, P D; Passingham, R E

    1999-11-01

    Anatomical studies in non-human primates have shown that the cerebellum has prominent connections with the dorsal, but not the ventral, visual pathways of the cerebral cortex. Recently, it has been shown that the dorsolateral prefrontal cortex (DPFC) and cerebellum are interconnected in monkeys. This has been cited in support of the view that the cerebellum may be involved in cognitive functions, e.g. working memory. Six monkeys (Macaca fascicularis) were therefore trained on a classic test of working memory, the spatial delayed alternation (SDA) task, and also on a visual concurrent discrimination (VCD) task. Excitotoxic lesions were made in the lateral cerebellar nuclei, bilaterally, in three of the animals. When retested after surgery the lesioned animals were as quick to relearn both tasks as the remaining unoperated animals. However, when the response times (RT) for each task were directly compared, on the SDA task the monkeys with cerebellar lesions were relatively slow to decide where to respond. We argue that on the SDA task animals can prepare their responses between trials whereas this is not possible on the VCD task, and that the cerebellar lesions may disrupt this response preparation. We subsequently made bilateral lesions in the DPFC of the control animals and retested them on the SDA task. These monkeys failed to relearn the task. The results show that, unlike the dorsal prefrontal cortex, the cerebellum is not essential for working memory or the executive processes that are necessary for correct performance, though it may contribute to the preparation of responses.

  18. Clinical and Subclinical Femoral Vascular Complications after Deployment of two Different Vascular Closure Devices or Manual Compression in the Setting of Coronary Intervention

    PubMed Central

    Yeni, Hakan; Axel, Meissner; Örnek, Ahmet; Butz, Thomas; Maagh, Petra; Plehn, Gunnar

    2016-01-01

    Background: In the past two decades vascular closure devices (VCD) have been increasingly utilized as an alternative to manual compression after percutaneous femoral artery access. However, there is a lack of data confirming a significant reduction of vascular complication in a routine interventional setting. Systematic assessment of puncture sites with ultrasound was hardly performed. Methods: 620 consecutive patients undergoing elective or urgent percutaneous coronary intervention were randomly allocated to either Angioseal (AS; n = 210), or Starclose (SC; n = 196) or manual compression (MC; n = 214). As an adjunct to clinical evaluation vascular ultrasonography was used to assess the safety of each hemostatic method in terms of major and minor vascular complications. The efficacy of VCDs was assessed by achievement of puncture site hemostasis. Results: No major complications needing transfusion or vascular surgery were observed. Furthermore, the overall incidence of clinical and subclinical minor complications was similar among the three groups. There was no differences in the occurrence of pseudoaneurysmata (AS = 10; SC = 6; MC = 10), arteriovenous fistula (AS = 1; SC = 4; MC = 2) and large hematoma (AS = 11; SC = 10; MC = 14). The choice of access site treatment had no impact in the duration of hospital stay (AS = 6.7; SC = 7.4; MS = 6.4 days). Conclusions: In the setting of routine coronary intervention AS and SC provide a similar efficacy and safety as manual compression. Subclinical vascular injuries are rare and not related to VCD use. PMID:27076781

  19. The role of chirality in a set of key intermediates of pharmaceutical interest, 3-aryl-substituted-γ-butyrolactones, evidenced by chiral HPLC separation and by chiroptical spectroscopies.

    PubMed

    Rossi, Daniela; Nasti, Rita; Collina, Simona; Mazzeo, Giuseppe; Ghidinelli, Simone; Longhi, Giovanna; Memo, Maurizio; Abbate, Sergio

    2017-01-05

    The enantiomers of four chiral 3-aryl-substituted-γ-butyrolactones, key intermediates for the preparation of compounds of pharmaceutical interest, were successfully isolated by enantioselective chromatography, employing the Chiralpak AD-H chiral stationary phase. For all compounds the same elution order was observed, as monitored by a full set of chiroptical methods that we employed, namely ORD (optical rotatory dispersion), ECD (electronic circular dichroism, or CD in the UV range), and VCD (vibrational circular dichroism, or CD in the IR range). By density functional theory (DFT) calculations we were able to determine that the first eluted enantiomer has (S) absolute configuration in all four cases. We were able to justify the elution order by molecular docking calculations for all four enantiomeric pairs and suitable modeling of the stationary and mobile phases of the employed columns. The optimal performance of the chiroptical spectroscopies and of the DFT calculations allows us to formulate a lactone chirality rule out of the CO stretching region of the VCD spectra.

  20. (TFPP)Eu[Pc(OPh)8]Eu[Pc(OPh)8]/CuPc two-component bilayer heterojunction-based organic transistors with high ambipolar performance.

    PubMed

    Gao, Dameng; Zhang, Xia; Kong, Xia; Chen, Yanli; Jiang, Jianzhuang

    2015-02-04

    Organic thin film transistor (OTFT) devices fabricated by the solution-based QLS technique from a mixed (phthalocyaninato)(porphyrinato) europium complex (TFPP)Eu[Pc(OPh)8]Eu[Pc(OPh)8] exhibit air-stable ambipolar performance with mobilities of 6.0 × 10(-5) cm(2) V(-1) s(-)1 for holes and 1.4 × 10(-4) cm(2) V(-1) s(-1) for electrons, respectively. In good contrast, the two-component bilayer heterojunction thin film devices constructed by directly growing (TFPP)Eu[Pc(OPh)8]Eu[Pc(OPh)8] on vacuum deposited (VCD) CuPc film using solution based QLS method were revealed to show unprecedented ambipolar performance with carrier mobilities of 0.16 cm(2) V(-1) s(-1) for holes and 0.30 cm(2) V(-1) s(-1) for electrons. In addition to the intrinsic role of p-type organic semiconductor, the VCD CuPc film on the substrate also acts as a good template that induces significant improvement over the molecular ordering of triple-decker compound in the film. In particular, it results in the change in the aggregation mode of (TFPP)Eu[Pc(OPh)8]Eu[Pc(OPh)8] from J-type in the single-layer film to H-type in the bilayer film according to the UV-vis, XRD, and AFM observations.

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

    SciTech Connect

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

    2016-07-25

    We investigated the stability and electronic properties of defects in CdTe 1- 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 CdTe 1- xSx increases with the S concentration as the valence band edge decreases with the S concentration, resulting in the reduced p-type doping efficiency.

  2. 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.

  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. Impacts of Recent Perennial Sea Ice Reduction on BrO Observations at Barrow, Alaska

    NASA Astrophysics Data System (ADS)

    Peterson, P.; Simpson, W. R.; Donohoue, D.; Nghiem, S. V.; Friess, U.; Platt, U.

    2013-12-01

    Polar sunrise in the Arctic has been associated with production of reactive halogens from sea salt(e.g. Br, BrO). While effects of these halogen species are well known(e.g. ozone depletion, mercury deposition), their production is not fully understood, but thought to be linked to heterogeneous chemistry taking place on saline ice surfaces(e.g saline snow, first year sea ice). Given the recent decline of perennial sea ice in the Arctic, it is imperative to understand the role of younger, more saline, first year ice in halogen activation processes. We used multiple axis differential optical absorption spectroscopy(MAX-DOAS) at Barrow, Alaska to observe BrO during the spring/early summer of 2008,2009,2012, and 2013. While average BrO boundary layer vertical column densities(BL-VCD) agreed within error during 2008 and 2009, the average observed BL-VCD doubled from 1e13 mol/cm^2 in 2008 and 2009, to 2e13 mol/cm^2 in 2012. We explore potential explanations for this observed increase using satellite maps of synoptic sea ice classes, MODIS imagery of local sea ice features, and back trajectory modelling. Potential impacts of the 2012 record minimum sea ice extent on observed halogen activation during the spring of 2013 are also discussed.

  5. 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.

  6. 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

    2015-11-01

    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.

  7. Water vapor retrieval from OMI visible spectra

    NASA Astrophysics Data System (ADS)

    Wang, H.; Liu, X.; Chance, K.; Gonzalez Abad, G.; Miller, C. Chan

    2014-01-01

    There are distinct spectral features of water vapor in the wavelength range covered by the Ozone Monitoring Instrument (OMI) visible channel. Although these features are much weaker than those at longer wavelengths, they can be exploited to retrieve useful information about water vapor. They have an advantage in that their small optical depth leads to fairly simple interpretation as measurements of the total water vapor column density. We have used the Smithsonian Astrophysical Observatory (SAO)'s OMI operational retrieval algorithm to derive the Slant Column Density (SCD) of water vapor from OMI measurements using the 430-480 nm spectral region after extensive optimization of retrieval windows and parameters. The Air Mass Factor (AMF) is calculated using look-up tables of scattering weights and monthly mean water vapor profiles from the GEOS-5 assimilation products. We convert from SCD to Vertical Column Density (VCD) using the AMF and generate associated retrieval averaging kernels and shape factors. Our standard water vapor product has a median SCD of ~ 1.3 × 1023 molecule cm-2 and a median relative uncertainty of ~ 11% in the tropics, about a factor of 2 better than that from a similar OMI algorithm but using narrower retrieval window. The corresponding median VCD is ~ 1.2 × 1023 molecule cm-2. We have also explored the sensitivities to various parameters and compared our results with those from the Moderate-resolution Imaging Spectroradiometer (MODIS) and the Aerosol Robotic NETwork (AERONET).

  8. 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

  9. 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.

  10. Enhancement of fluorescence in anthracene by chlorination: Vibronic coupling and transition dipole moment density analysis

    NASA Astrophysics Data System (ADS)

    Uejima, Motoyuki; Sato, Tohru; Tanaka, Kazuyoshi; Kaji, Hironori

    2014-02-01

    The vibronic coupling constants and transition dipole moments for the Franck-Condon and adiabatic S1 states of anthracene, 9-chloroanthracene, and 9,10-dichloroanthracene were calculated and analyzed by using the concept of vibronic coupling density (VCD). The transition dipole moments are also analyzed on the basis of the transition dipole moment density (TDMD). The VCD analyses indicate that the vibronic couplings in the Franck-Condon S1 state come from the side rings of anthracene, and introduction of chlorine atoms reduces the vibronic couplings in the side regions and the reorganization energy. The TDMD analyses indicate that the chlorination enhances the transition dipole moment and that the contribution of the chlorine atom to the transition dipole moment is the largest. Finally, we derived a design principle for anthracene derivatives with a high quantum yield: the same long acceptors should be introduced into the two central carbon atoms in the anthracene's central ring for the derivative to keep the point group to be D2h.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Chiral recognition by fullerenes: CHFClBr enantiomers in the C82 cage.

    PubMed

    Dodziuk, Helena; Ruud, Kenneth; Korona, Tatiana; Demissie, Taye B

    2016-09-21

    Density-functional theory and symmetry-adapted perturbation theory calculations on complexes of the enantiomers of CHFClBr with the most stable isomer of C82-3 fullerene show that despite the guests being too large for the host cage, they are nevertheless stabilized by electrostatic interactions. The complexation leads to considerable strain on the cage and the guests accompanied by compression of the bonds of the guest molecule, resulting in considerable complexation-induced changes in the infrared (IR), vibrational circular dichroism (VCD), nuclear magnetic resonance (NMR), and UV-vis spectra. The effect of chiral recognition is pronounced only for the (19)F signal in the NMR spectra and in a sign reversal of the rotational strength of the νCH stretching vibration of S-CHFClBr@C82-3 in the VCD spectrum as compared to that of the free guest, making the sign of this band for the C82 complexes with the S- and R-guest enantiomers the same. This is a surprising result since vibrational circular dichroism is considered a reliable method for determining the absolute chirality of small molecules and for establishing dominant conformations in biopolymers.

  14. Ultrasonographic and macroscopic anatomy of the enucleated eyes of the buffalo (Bos bubalis) and the one-humped camel (Camelus dromedarius) of different ages.

    PubMed

    Kassab, A

    2012-02-01

    The ultrasonographic appearance and measurements of the normal buffalo and camel eye globes were described in 60 buffaloes (Bos bubalis) aged 1 year (28 eyes) and 10 years (32 eyes), and in 51 humped camels (Camelus dromedarius) aged 1 year (26 eyes) and 10 years (24 eyes). Ocular measurements were recorded by A- and B-scan ultrasonographic examination of 40 buffalo eyes (18 young and 22 adult eyes) and 34 camel eyes (14 young and 20 adult eyes) using a KANGH ultrasound scanner equipped with 10 MHz probe. For gross measurements, 20 buffalo and 16 camel eye globes were frozen and dissected and the same measurements were made using fine callipers macroscopically. The aqueous and vitreous humour of the buffalo and camel eyes appeared anechoic. The cornea, anterior and posterior lens capsule and iris appeared hyperechoic. The ocular measurements for the axial length, vitreous chamber depth (VCD), corneal thickness, lens thickness and scleroretinal rim thickness increase with the advance of age in both buffaloes and camels. Except for the anterior chamber depth, VCD and lens thickness, which were larger in adult camels than in adult buffaloes, no other differences between ocular dimensions were observed in both species. The results of this study are valuable for comparative ocular anatomy and will be useful for ultrasonographic evaluation of ocular diseases in buffaloes and camels.

  15. The Correlation of Differences in the Ocular Component Values with the Degree of Myopic Anisometropia

    PubMed Central

    Kim, Su-Young; Cho, Soon Young; Yang, Ji Wook; Kim, Chan Su

    2013-01-01

    Purpose To determine the relationship between the differences in the ocular component values with the degree of anisomyopia. Methods Refraction, corneal power (CP), and biometry were examined in 50 myopic adults with refractive differences (RD) over 1.50 diopters (D). Ocular components were measured by ultrasound biometry and keratometry. The correlation between the differences in the ocular component values with the degree of anisomyopia was analyzed by linear regression analysis. Results Among 50 adults with anisomyopia, 5 had RD from 1.50 to 2.99 D, 11 had RD from 3.00 to 3.99 D, 9 had RD from 4.00 to 5.99 D, 12 had RD from 6.00 to 7.99 D, 7 had RD from 8.00 to 11.99 D, and 6 had ≥12.00 D. There was no significant correlation between the ocular components (CP, crystalline lens thickness [LT], and anterior chamber depth [ACD], and the length from the cornea to the posterior surface of the lens [ACD + LT]) and the RD (p > 0.05). The RD showed a significantly positive correlation with vitreous chamber depth (VCD), and axial length (r = 0.963, p < 0.0001). Conclusions The severity of anisomyopia was not correlated with the between-eye differences in the anterior chamber values of the eye (CP, ACD, LT, ACD + LT). The severity of anisomyopia was significantly correlated with the between-eye differences in VCD. PMID:23372379

  16. Comprehensive spectroscopic characterization of finasteride polymorphic forms. Does the form X exist?

    PubMed

    Frelek, Jadwiga; Górecki, Marcin; Dziedzic, Alicja; Jabłońska, Ewa; Kamieński, Bohdan; Wojcieszczyk, Ryszard K; Luboradzki, Roman; Szczepek, Wojciech J

    2015-05-01

    The pure polymorphic forms I, II, and III of finasteride were prepared and their purity was confirmed by FTIR, differential scanning calorimetry, and X-ray powder diffraction measurements. The preparation experiments demonstrated that the desolvation process of some finasteride solvates does result not only in the formation of polymorphic forms I and II, but also in obtaining the pure form III. The (13)C cross-polarization magic angle spinning (CP-MAS) and the (15)N CP-MAS spectra can distinguish all three polymorphic forms of finasteride. Additionally, the data point to the presence of only one molecule in crystallographic asymmetric unit of polymorphic forms I and III and two molecules in the form II. The application of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectroscopy for finasteride polymorphic forms shows that the three polymorphs could be distinguished by the characteristic shapes of their VCD spectra in the spectral range 1520-1440 cm(-1). The ECD spectral patterns of all these forms, however, are almost indistinguishable because of their close similarity. Comparison of the (13)C CP-MAS spectra of forms I, II, and III with those reported in the literature indicates that the so-called finasteride "form X" is identical to the previously known finasteride form III. On this basis, the existence of form X was excluded.

  17. DNA oligonucleotide-cis-platin binding: Ab initio interpretation of the vibrational spectra.

    PubMed

    Andrushchenko, Valery; Wieser, Hal; Bour, Petr

    2007-10-04

    The cis-platin binding to the d(CCTGGTCC)*d(GGACCAGG) model DNA octamer was monitored with infrared absorption (IR) and vibrational circular dichroism (VCD) spectroscopies. The spectra were modeled with the aid of density functional computations and a Cartesian coordinate-based transfer of molecular property tensors from smaller DNA fragments. Because of the fragmentation, the tensors could be calculated with a higher precision. Environmental effects, such as the presence of the solvent or the cis-platin ligand, could be included in the modeling. The solvent was modeled by an explicit inclusion of hydrogen-bound water molecules, positions of which were estimated from a molecular dynamics simulation, or by the polarized continuum COSMO model. The B3LYP and BPW91 functionals used for the calculations of the spectral parameters were combined with the relativistic LANL2DZ platinum pseudo-potentials. The simulations reproduced the main IR and VCD DNA spectral features and explained most of the changes observed experimentally upon metal binding. The results confirmed that the influence of the ligand on DNA vibrational properties is quite complex; it originates in the geometry deformation and normal mode coupling pattern changes of the platinated octamer, as well as in local perturbations of the electronic structure and force field of the GC base pairs to which the platinum is bound. Many of the local effects could be accounted for by a point charge used in place of the metal in the GC complex.

  18. Spectroscopic, thermal and structural studies of new L-leucine and D-leucine complexes with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Pawlukojć, A.; Hetmańczyk, J.; Nowicka-Scheibe, J.; Maurin, Jan K.; Schilf, W.; Rozwadowski, Z.

    2017-04-01

    New molecular complexes of L-leucine and D-leucine with chloranilic acid have been synthesized. Crystal structures of these crystals have been solved; they crystallize in non-centrosymmetric monoclinic P21 space group. In the crystal, leucine molecules exist in protonated form (C6NO2H14+) and chloranilic acid molecules in deprotonated form (C6HCl2O4-). Electronic (UV-Vis) and vibrational absorption (VA) spectra for both materials were collected. Circular dichroism methods such as electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were used to determine the absolute configuration of new complexes. In both methods a characteristic (-,+) Cotton patterns are observed. In ECD spectra absorption bands are observed at 212 nm for acetonitrile solution and at 202 nm for aqueous solution. VCD spectra (in DMSO-d6 solution) show (-,+) Cotton pattern with strong peaks at 1323 cm-1 (CH rocking mode). Differential scanning calorimetry (DSC) and thermogravimetric (TG) investigations were performed to explore thermal properties of new materials. In DSC curve the decomposition and combustion processes are observed in 220-227 °C. The decomposition process was described by use of TG method and quadruple mass spectrometer (QMS). NMR spectra of pure L-leucine and chloranilic acid as well as L-leucine - chloranilic acid complex in solutions (D2O and DMSO) and in solid state confirm the geometry of molecules in complex both in solution and in solid state.

  19. 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.

  20. 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

    2008-04-07

    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.

  1. Epoxy resin monomers with reduced skin sensitizing potency.

    PubMed

    O'Boyle, Niamh M; Niklasson, Ida B; Tehrani-Bagha, Ali R; Delaine, Tamara; Holmberg, Krister; Luthman, Kristina; Karlberg, Ann-Therese

    2014-06-16

    Epoxy resin monomers (ERMs), especially diglycidyl ethers of bisphenol A and F (DGEBA and DGEBF), are extensively used as building blocks for thermosetting polymers. However, they are known to commonly cause skin allergy. This research describes a number of alternative ERMs, designed with the aim of reducing the skin sensitizing potency while maintaining the ability to form thermosetting polymers. The compounds were designed, synthesized, and assessed for sensitizing potency using the in vivo murine local lymph node assay (LLNA). All six epoxy resin monomers had decreased sensitizing potencies compared to those of DGEBA and DGEBF. With respect to the LLNA EC3 value, the best of the alternative monomers had a value approximately 2.5 times higher than those of DGEBA and DGEBF. The diepoxides were reacted with triethylenetetramine, and the polymers formed were tested for technical applicability using thermogravimetric analysis and differential scanning calorimetry. Four out of the six alternative ERMs gave polymers with a thermal stability comparable to that obtained with DGEBA and DGEBF. The use of improved epoxy resin monomers with less skin sensitizing effects is a direct way to tackle the problem of contact allergy to epoxy resin systems, particularly in occupational settings, resulting in a reduction in the incidence of allergic contact dermatitis.

  2. 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.

  3. 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.

  4. 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

  5. Crosslinked redox polymer enzyme electrodes containing carbon nanotubes for high and stable glucose oxidation current.

    PubMed

    MacAodha, Domhnall; Ferrer, Maria Luisa; Conghaile, Peter Ó; Kavanagh, Paul; Leech, Dónal

    2012-11-14

    Co-immobilisation approaches for preparation of glucose-oxidising films of [Os(2,2'-bipyridine)(2)(poly-vinylimidazole)(10)Cl] and glucose oxidase on glassy carbon electrodes are compared. Electrodes prepared by crosslinking using glutaraldehyde vapour, without and with a NaBH(4) reduction, provide higher glucose oxidation current than those prepared using a well-established diepoxide method. Addition of multi walled carbon nanotubes to the film deposition solutions produces an enhanced glucose oxidation current density of 5 mA cm(-2) at 0.35 V vs. Ag/AgCl, whilst improving the operational stability of the current signal. Carbon nanotube, glutaraldehyde vapour crosslinked, films on electrodes, reduced by NaBH(4), retain 77% of initial catalytic current over 24 hours of continuous amperometric testing in a 37 °C, 50 mM phosphate buffer solution containing 150 mM NaCl and 100 mM glucose. Potential application of this approach to implantable enzymatic biofuel cells is demonstrated by production of glucose oxidation currents, under pseudo-physiological conditions, using mediating films with lower redox potentials.

  6. 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

  7. 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

  8. Size reduction of CdSe/ZnS quantum dots by a peptidic amyloid supergelator.

    PubMed

    Zaman, Md Badruz; Bardelang, David; Prakesch, Michaël; Leek, Donald M; Naubron, Jean-Valère; Chan, Gordon; Wu, Xiaohua; Ripmeester, John A; Ratcliffe, Christopher I; Yu, Kui

    2012-03-01

    Anchoring of a self-assembling dipeptide on the surface of core/shell CdSe/ZnS quantum dots resulted in a competition between coordination of the surface atoms of the QDs and the strong tendency for the dipeptide to self-assemble in toluene. This resulted in a mild QD etching and in a corresponding increase in the band gap of the nanocrystals whose photoluminescent emission gradually turns blue with time. The FmocLeuLeuOH dipeptide supergelator self-assembles in fibrils in which the Fmoc groups are surrounded by the pendant isobutyl side chains of the leucine residues with vibrational circular dichroism (VCD) and liquid- and solid-state NMR attributes of twist anti-parallel β-sheets.

  9. 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.

  10. Deep level transient spectroscopy investigation of deep levels in CdS/CdTe thin film solar cells with Te:Cu back contact

    NASA Astrophysics Data System (ADS)

    Wang, Zhao; Li, Bing; Zheng, Xu; Xie, Jing; Huang, Zheng; Liu, Cai; Feng, Liang-Huan; Zheng, Jia-Gui

    2010-02-01

    Deep levels in Cds/CdTe thin film solar cells have a potent influence on the electrical property of these devices. As an essential layer in the solar cell device structure, back contact is believed to induce some deep defects in the CdTe thin film. With the help of deep level transient spectroscopy (DLTS), we study the deep levels in CdS/CdTe thin film solar cells with Te:Cu back contact. One hole trap and one electron trap are observed. The hole trap H1, localized at Ev + 0.128 eV, originates from the vacancy of Cd (VCd). The electron trap E1, found at Ec -0.178 eV, is considered to be correlated with the interstitial Cuj+ in CdTe.

  11. 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.

  12. Absolute Configuration Assignment of 3',4'-di-O-acylkhellactones Using Vibrational Circular Dichroism Exciton Chirality.

    PubMed

    Buendía-Trujillo, Abigail I; Torrres-Valencia, J Martín; Joseph-Nathan, Pedro; Burgueño-Tapia, Eleuterio

    2015-06-01

    The 3'R,4'R absolute configuration (AC) of the angular-type pyranocoumarins (-)-3',4'-di-O-acetylkhellactone (2), (-)-4'-O-acetyl-3'-O-angeloylkhellactone (3), (+)-3'-O-acetyl-4'-O-isobutyroylkhellactone (4), and (-)-3'-O-angeloyl-4'-O-senecioylkhellactone (5), isolated from the aerial parts of Prionosciadium thapsoides, was assigned by vibrational circular dichroism exciton chirality (VCDEC), and confirmed by comparison of their VCD frequencies with those calculated using DFT at the B3LYP/DGDZVP level. This again reveals that AC assignments based on optical rotation data are not very confident. Evaluation of Flack and Hooft parameters obtained after single-crystal X-ray diffraction analysis of 3, independently confirmed this AC.

  13. A new steel for single cylinder steam turbine rotors

    SciTech Connect

    Yamada, M.; Tsuda, Y.; Tanaka, Y.; Ikeda, Y.

    1996-12-31

    A new steel, 2.25%Cr1.7%NiMoVNbW steel has been developed for the high pressure (HP)-low pressure (LP) single cylinder steam turbine rotor in combined power plants and medium/small rating thermal power plants. This steel has good creep rupture strength equivalent to that of 1%CrMoV steel which has been used as HP rotor fogings and excellent toughness and proof stress considerably superior to the conventional HP-LP single cylinder rotor steels. This paper includes the following contents: The optimization of chemical composition and heat treatment condition; the production and evaluation of a 70 tons trial rotor forging by the application of VCD (Vacuum Carbon Deoxidation) process; the production and evaluation of a 43 tons trial ingot by the application of ESR (Electroslag Remelting) ingot process; and the production and evaluation of rotor forgings for the commercial power plant.

  14. 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

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-05-01

    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.

  17. 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.

  18. Estimation of NO2 emissions from Lahore and Rawalpindi / Islamabad using Car MAX-DOAS observations and comparison with OMI satellite data

    NASA Astrophysics Data System (ADS)

    Razi, Maria; Fahim Khokhar, Muhammad; Javed, Zeeshan; Ahmad, Noor; Wagner, Thomas

    2015-04-01

    We present results of ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements performed around the cities of Lahore and Rawalpindi / Islamabad, Pakistan and also between the cities along National Highway, N5. From the car-MAX-DOAS measurements, the tropospheric vertical column density (VCD) of NO2 is retrieved based on the so called geometric approximation. Based on observations along large circles around the cities and wind data we estimate the NO2 emissions from the cities of Lahore and Rawalpindi / Islamabad. We also compare the spatial distributions of the tropospheric NO2 VCDs observed by car MAX-DOAS with collocated results from the satellite based Ozone Monitoring Instrument (OMI). We discuss the influence of the observed spatial gradients on the comparison between both data sets.

  19. 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.

  20. Chiral mononuclear lanthanide complexes and the field-induced single-ion magnet behaviour of a Dy analogue.

    PubMed

    Lin, Shuang-Yan; Wang, Chao; Zhao, Lang; Wu, Jianfeng; Tang, Jinkui

    2015-01-07

    Three pairs of homochiral mononuclear lanthanide complexes, with the general formula [LnH4LRRRRRR/SSSSSS(SCN)2](SCN)2·xCH3OH·yH2O(Ln = Dy (R/S-Dy1), Ho (R/S-Ho1) and Er (R/S-Er1)), have been obtained via self-assembly between chiral macrocyclic ligands and the respective thiocyanates, all of which show a saddle-type conformation with seven-coordinated metal ions. Magnetic measurements revealed that the Dy complex shows field-induced single-ion magnet behaviour, which is rarely reported in a seven-coordinated lanthanide-based SIM encapsulated in a macrocyclic ligand. The absolute configuration of all enantiomers was determined by single crystal X-ray crystallography and confirmed by electronic CD and VCD spectra.

  1. An analysis of point defects induced by In, Al, Ni, and Sn dopants in Bridgman-grown CdZnTe detectors and their influence on trapping of charge carriers

    NASA Astrophysics Data System (ADS)

    Gul, R.; Roy, U. N.; James, R. B.

    2017-03-01

    In this research, we studied point defects induced in Bridgman-grown CdZnTe detectors doped with Indium (In), Aluminium (Al), Nickel (Ni), and Tin (Sn). Point defects associated with different dopants were observed, and these defects were analyzed in detail for their contributions to electron/hole (e/h) trapping. We also explored the correlations between the nature and abundance of the point defects with their influence on the resistivity, electron mobility-lifetime (μτe) product, and electron trapping time. We used current-deep level transient spectroscopy to determine the energy, capture cross-section, and concentration of each trap. Furthermore, we used the data to determine the trapping and de-trapping times for the charge carriers. In In-doped CdZnTe detectors, uncompensated Cd vacancies (VCd-) were identified as a dominant trap. The VCd- were almost compensated in detectors doped with Al, Ni, and Sn, in addition to co-doping with In. Dominant traps related to the dopant were found at Ev + 0.36 eV and Ev + 1.1 eV, Ec + 76 meV and Ev + 0.61 eV, Ev + 36 meV and Ev + 0.86 eV, Ev + 0.52 eV and Ec + 0.83 eV in CZT:In, CZT:In + Al, CZT:In + Ni, and CZT:In + Sn, respectively. Results indicate that the addition of other dopants with In affects the type, nature, concentration (Nt), and capture cross-section (σ) and hence trapping (tt) and de-trapping (tdt) times. The dopant-induced traps, their corresponding concentrations, and charge capture cross-section play an important role in the performance of radiation detectors, especially for devices that rely solely on electron transport.

  2. Comparison of digital and film stereo photography of the optic nerve in the evaluation of patients with glaucoma.

    PubMed

    Khouri, Albert S; Szirth, Bernard; Realini, Tony; Fechtner, Robert D

    2006-12-01

    The aim of this study was to validate a digital simultaneous stereo photography system against film in the assessment of optic nerve head features in patients with glaucoma. Fifteen digital and 15 corresponding film simultaneous stereo photographs (SSP) of the optic nerve from patients with glaucoma were graded by two glaucoma specialists. Assessed parameters included the vertical and horizontal cup-to-disc ratios (VCD and HCD, respectively), and the image quality score (1 = worse, 5 = best) for each image. Digital and film SSP were presented in random order, two times to each grader. A total of 60 evaluations (30 digital and 30 film) per grader were collected. A Nidek 3-Dx simultaneous stereo disc camera (Gamagori, Japan) was used with both a standard 35-mm-film camera back, and with a 6.1 mega pixel camera (Nikon D1x, Tokyo, Japan) for capture of digital images. All digital images were stored on a computer and reviewed using the Navis Screener software (proprietary software from Nidek). Digital image pairs were evaluated directly on an ADVAN 27-inch Liquid Crystal Display computer monitor (Taipei, Taiwan) with resolution comparable to that of the digital camera, using the screen-vu stereo viewer held at a fixed angle to the monitor. Film image pairs were evaluated using a Pentax stereo slide viewer (Asahi Optical Co., Tokyo, Japan) illuminated by a light box over a neutral density filter to match the luminance between the computer screen and the light box. The mean difference between digital and film was near zero for all three evaluated outcomes (VCD, HCD, and quality score), and there was no significant grader effect for any of the outcomes. Digital images correlated well with film for SSP of the optic nerve in glaucoma.

  3. Investigation of structural defects in In-doped CdZnTe under different in-situ annealing cooling rates

    NASA Astrophysics Data System (ADS)

    Xing, Xiaobing; Min, Jiahua; Liang, Xiaoyan; Zhang, Jijun; Wang, Linjun; Yang, Liuqing; Ling, Yunpeng; Duan, Lei; Shen, Yue

    2015-09-01

    The In-doped Cd0.9Zn0.1Te (CZT) crystals were grown by the modified Vertical Bridgeman method and treated by in-situ annealing with six different cooling rates. Photo-Induced Transient Spectroscopy (PICTS) and IR microscopy were employed to investigate the evolution mechanism of point defects and bulk defects (mainly Te inclusions) in the CZT crystals with different cooling rates. Related optical and electrical properties were investigated by Fourier Transform Infrared Spectrometer (FTIR) and I-V measurements. The results indicated that cooling at slow rate (10-20 K/h) could decrease the concentration of point defects, such as A center, Cd vacancy (VCd2-), Te antisite (TeCd2+) and so on, while the Te inclusions are of larger dimension and lower concentration. Otherwise, the faster cooling rate (50-60 K/h), the higher concentration of these point defects, and Te inclusion present small size but much larger concentration. Moreover, cooling too fast or too slow significantly degrades the optical and electrical properties. When cooled at 30-40 K/h, the concentration of internal point defects is the lowest, suggesting that VCd2- compensated with TeCd2+ to reach a new equilibrium corresponding to the theory of quasichemical defect reactions (QCDR). In addition, a certain concentration of TeCd2+ was beneficial to pin the Fermi-level, and the Te inclusions presented lowest total volume fraction, which made the crystals perform great with higher resistivity and infrared transmittance.

  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.

  5. On determination of formaldehyde content in atmospheric boundary layer for overcast using DOAS technique

    NASA Astrophysics Data System (ADS)

    Postylyakov, Oleg; Borovski, Alexander; Ivanov, Victor

    2015-11-01

    Formaldehyde (HCHO) is involved in a lot of chemical reactions in the atmosphere. Taking into account that HCHO basically undergo by photolysis and reaction with hydroxyl radical within a few hours, short-lived VOCs and direct HCHO emissions can cause local HCHO enhancement over certain areas, and, hence, exceeding background level of HCHO can be examined as a local pollution of the atmosphere by VOCs or existence of a local HCHO source. Several retrieval algorithms applicable for DOAS measurements in cloudless were previously developed. A new algorithm applicable for overcast and cloudless sky and its error analysis is briefly introduced by this paper. Analysis of our HCHO VCD retrieval for overcast shows that when one know the cloud base height, but doesn't know cloud optical depth, the typical errors of HCHO total content retrieval are less than 10% for snow season, less than 5% for snow-free seasons, and reaches 40-45% for season with non-stable snow cover. In case one knows both the cloud base height and the cloud optical depth, the typical errors are about 5% for snow season, less than 2.5% for snow-free seasons, and are within about 10-30% for season with non-stable snow cover. Given above error estimations are valid if the HCHO layer is below the cloud base. The errors dramatically increase when HCHO layer penetrates into clouds in both cases. The first preliminary results of HCHO VCD retrieval for overcast are shown. The average difference of the HCHO VCDs for wind from Moscow megapolis and wind from few urbanized areas is about 0.8×1016 mol×cm-2 and approximately corresponds to estimates of influence of Moscow megapolis observed in clear-sky conditions.

  6. Variability of bromine monoxide at Barrow, Alaska, over four halogen activation (March-May) seasons and at two on-ice locations

    NASA Astrophysics Data System (ADS)

    Peterson, Peter K.; Simpson, William R.; Nghiem, Son V.

    2016-02-01

    Reactive halogens profoundly influence springtime Arctic atmospheric chemistry, but their relationship to sea ice and environmental conditions is not well understood. Multiple axis differential optical absorption spectroscopy measured bromine monoxide (BrO) at Barrow, Alaska, and at two Arctic Ocean buoys. For each season of Barrow measurements, we examined the air mass histories using back trajectory modeling and ice coverage maps. We find a weak positive linear correlation (R = 0.38) between half-hourly BrO lower tropospheric vertical column densities (LT-VCD) and time in first year sea ice (FYI) areas. These data show evidence of a nonlinear increase of LT-VCD BrO with low-average column in the absence of ice contact, with the column increasing and saturating at ice contact longer than ≈1.5 days. We find that trajectories arriving at Barrow are dominated by FYI area influence with little multiyear ice (MYI) area contact; therefore, this study cannot make any conclusions regarding MYI area influences on reactive halogen production. Contact with calculated potential frost flower influence is not correlated with BrO column (R = 0.04). At Barrow, annual averages of BrO column over the halogen activation season and time in FYI areas are highly correlated (R = 0.93, significant at 90% confidence), which is interpreted as an effect of interannual transport variability. At on-ice locations, we observe a wide range of BrO LT-VCDs, suggesting that while an air mass spending time in sea ice areas is required to observe significant BrO, sea ice contact alone does not imply high BrO, and other environmental controls are important.

  7. 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.

  8. Vector-spin-chirality order in a dimerized frustrated spin-1/2 chain

    NASA Astrophysics Data System (ADS)

    Ueda, Hiroshi; Onoda, Shigeki

    2014-01-01

    A frustrated spin-1/2 XXZ chain model comprising a ferromagnetic nearest-neighbor coupling with the bond alternation, J1(1±δ)<0, and an antiferromagnetic second-neighbor exchange coupling J2>0 is studied at zero and weak magnetic fields by means of density-matrix renormalization-group calculations of order parameters, correlation functions, and the entanglement entropy, as well as an Abelian bosonization analysis. At zero magnetic field, the bond alternation δ >0 suppresses the gapless phase characterized by a vector-chiral (VC) long-range order (LRO) and a quasi-LRO of an incommensurate spin spiral, whereas this phase occupies a large region in the space of J1/J2 and the easy-plane exchange anisotropy for δ =0 [S. Furukawa et al., Phys. Rev. Lett. 105, 257205 (2010), 10.1103/PhysRevLett.105.257205]. Then, four gapped phases are found to appear as the exchange anisotropy varies from the SU(2)-symmetric case to the U(1)-symmetric case: the Haldane dimer (D+) phase with the same sign of the x ,y- and z-component dimer order parameters, two VC dimer (VCD+/VCD-) phases with the sign of the z-component dimer order parameter being unaltered/reversed, and the even-parity dimer (D-) phase. At small magnetic fields, a field-induced ring-exchange interaction, which is proportional to a staggered scalar chirality and a magnetic flux penetrating the associated triangle, drives a transition from the D- phase into a VC-Neel-dimer (VCND) phase, but not from the D+ phase. This VCND phase is stable up to the large magnetic field at which the Zeeman term closes the spin gap. A possible relevance to Rb2Cu2Mo3O12 is discussed.

  9. The influence of polarization on box air mass factors for UV/vis nadir satellite observations

    NASA Astrophysics Data System (ADS)

    Hilboll, Andreas; Richter, Andreas; Rozanov, Vladimir V.; Burrows, John P.

    2015-04-01

    Tropospheric abundances of pollutant trace gases like, e.g., NO2, are often derived by applying the differential optical absorption spectroscopy (DOAS) method to space-borne measurements of back-scattered and reflected solar radiation. The resulting quantity, the slant column density (SCD), subsequently has to be converted to more easily interpretable vertical column densities by means of the so-called box air mass factor (BAMF). The BAMF describes the ratio of SCD and VCD within one atmospheric layer and is calculated by a radiative transfer model. Current operational and scientific data products of satellite-derived trace gas VCDs do not include the effect of polarization in their radiative transfer models. However, the various scattering processes in the atmosphere do lead to a distinctive polarization pattern of the observed Earthshine spectra. This study investigates the influence of these polarization patterns on box air mass factors for satellite nadir DOAS measurements of NO2 in the UV/vis wavelength region. NO2 BAMFs have been simulated for a multitude of viewing geometries, surface albedos, and surface altitudes, using the radiative transfer model SCIATRAN. The results show a potentially large influence of polarization on the BAMF, which can reach 10% and more close to the surface. A simple correction for this effect seems not to be feasible, as it strongly depends on the specific measurement scenario and can lead to both high and low biases of the resulting NO2 VCD. We therefore conclude that all data products of NO2 VCDs derived from space-borne DOAS measurements should include polarization effects in their radiative transfer model calculations, or at least include the errors introduced by using linear models in their uncertainty estimates.

  10. 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.

  11. 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.

  12. Evaluating the toxicity of bDtBPP on CHO-K1 cells for testing of single-use bioprocessing systems considering media selection, cell culture volume, mixing, and exposure duration.

    PubMed

    Shah, Rhythm R; Linville, Taylor W; Whynot, Andrew D; Brazel, Christopher S

    2016-09-01

    Single-use bioprocessing bags are gaining popularity due to ease of use, lower risk of contamination, and ease of process scale-up. Bis(2,4-di-tert-butylphenyl)phosphate (bDtBPP), a degradant of tris(2,4-di-tert-butylphenyl)phosphite, marketed as Irgafos 168®, which is an antioxidant stabilizer added to resins, has been identified as a potentially toxic leachate which may impact the performance of single-use, multilayer bioprocessing bags. In this study, the toxicity of bDtBPP was tested on CHO-K1 cells grown as adherent or suspended cells. The EC50 (effective concentration to cause 50% cell death) for adherent cells was found to be one order of magnitude higher than that for suspended CHO-K1 cells. While CHO-K1 cells had good cell viability when exposed to moderate concentrations of bDtBPP, the degradant was shown to impact the viable cell density (VCD) at much lower concentrations. Hence, in developing an industry-standard assay for testing the cytotoxicity of leachates, suspended cells (as commonly used in the bioprocessing industry) would likely be most sensitive, particularly when reporting EC50 values based on VCD. The effects of mixing, cell culture volume, and exposure duration were also evaluated for suspended CHO-K1 cells. It was found that the sensitivity of cell culture to leachates from single-use plastic bags was enhanced for suspended cells cultured for longer exposure times and when the cells were subjected to continuous agitation, both of which are important considerations in the production of biopharmaceuticals. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1318-1323, 2016.

  13. Using Vascular Closure Devices Following Out-Of-Hospital Cardiac Arrest?

    PubMed Central

    Christ, Martin; von Auenmueller, Katharina Isabel; Liebeton, Jeanette; Grett, Martin; Dierschke, Wolfgang; Noelke, Jan Peter; Breker, Irini Maria; Trappe, Hans-Joachim

    2015-01-01

    Objectives and Background: Despite a generally broad use of vascular closure devices (VCDs), it remains unclear whether they can also be used in victims from out-of-hospital cardiac arrest (OHCA) treated with mild therapeutic hypothermia (MTH). Methods: All victims from OHCA who received immediate coronary angiography after OHCA between January 1st 2008 and December 31st 2013 were included in this study. The operator decided to either use a VCD (Angio-Seal™) or manual compression for femoral artery puncture. The decision to induce MTH was based on the clinical circumstances. Results: 76 patients were included in this study, 46 (60.5%) men and 30 (39.5%) women with a mean age of 64.2 ± 12.8 years. VCDs were used in 26 patients (34.2%), and 48 patients (63.2%) were treated with MTH. While there were significantly more overall vascular complications in the group of patients treated with MTH (12.5% versus 0.0%; p=0.05), vascular complications were similar between patients with VCD or manual compression, regardless of whether or not they were treated with MTH. Conclusion: In our study, the overall rate of vascular complications related to coronary angiography was higher in patients treated with mild therapeutic hypothermia, but was not affected by the application of a vascular closure device. Therefore, our data suggest that the use of VCDs in victims from OHCA might be feasible and safe in patients treated with MTH as well, at least if the decision to use them is individually carefully determined. PMID:25897291

  14. Changes in choroidal thickness after prophylactic iridectomy in primary angle closure suspect eyes using enhanced depth imaging optical coherence tomography

    PubMed Central

    Wang, Wei; Zhou, Minwen; Huang, Wenbin; Gao, Xinbo; Zhang, Xiulan

    2015-01-01

    Purpose: The aim of the present study was to evaluate the effect of surgical peripheral iridectomy (SPI) on choroidal thickness in primary angle-closure suspect (PACS) eyes. Materials and Methods: This was a prospective observational case series of 30 subjects with PACS. Ocular biometry was performed before SPI (baseline) and then 1 week later. Choroid was imaged by enhanced depth imaging optical coherence tomography (EDI-OCT). The choroidal thickness of the subfoveal area at 1 and 3 mm diameter around the fovea was determined. Central anterior chamber depth (ACD), lens thickness (LT), vitreous chamber depth (VCD), and axial length (AL) were measured by A-scan ultrasound. Parameters were compared before SPI (baseline) and 1 week later. Results: Thirty eyes of 30 patients with mean age of 61.53 ± 7.98 years were studied. There was no significant difference in the choroidal thickness at all macular locations before and after SPI (all P > 0.05). Mean subfoveal choroidal thickness was 279.61 μm ± 65.50 μm before and 274.54 μm ± 63.36 μm after SPI (P = 0.308). There was also no significant change in central ACD, LT, VCD, and LT after SPI (all P > 0.05). Conclusions: SPI does not appear to alter choroidal thickness in PACS eyes, as assessed using EDI-OCT. Long-term follow-up of PACS eyes treated with SPI may provide further insight into the effects of this treatment modality on the choroid. PMID:26654999

  15. Molecular dynamics and reaction kinetics during polymerization using dielectric spectroscopy and calorimetry

    NASA Astrophysics Data System (ADS)

    Wasylyshyn, Dwayne Andrew

    The evolution of molecular dynamics during the polymerization of linear-chain and network forming liquids was studied using dielectric spectroscopy and differential scanning calorimetry. Polymerization was carried out using step-addition reactions between epoxide and amine molecules, and by catalysis of epoxide molecules with tertiary amines. The former resulted in linear-chain or network structured polymers while the latter resulted in network polymers. The step-addition polymerizations resulted in linear-chain polymers by reacting stoichiometric quantities of diepoxide and monoamine molecules, and network structure polymers by reacting stoichiometric quantities of triepoxide and monoamine molecules, or diepoxide and diamine molecules. The growth and extinction of localized (or secondary) relaxation processes during the polymerization were studied by measuring the changing dielectric properties using two techniques; fixed frequency dielectric measurements during heating of the partially polymerized samples, and isothermal dielectric measurements over the frequency range of 1 MHz to 20 GHz. The number of covalent bonds formed at any instant during the polymerization was determined by isothermal calorimetric measurements. Thus, the change in the dielectric properties during polymerization was associated with the increase in the number of covalent bonds. It was found that the localized relaxations evolve in a manner that is independent of the spontaneous increase in configurational entropy. The results also tend evidence towards the concept that these relaxations occur in regions of relatively high energy, and the collapse of such regions led to the observed changes in the dielectric properties. As well, an analogy was made between the structural relaxation of a physically metastable glass and the polymerization of a chemically metastable liquid. This has lead to the concept of a chemical fictive temperature to describe the state of the polymerizing liquid. The

  16. Study on thermally reworkable underfills for flip chip, BGA, and CSP applications

    NASA Astrophysics Data System (ADS)

    Wang, Lejun

    Underfill is a polymeric material used in the flip-chip devices that fills the gap between an integrated circuit (IC) chip and an organic printed wiring board (PWB), and encapsulates the solder interconnects. This underfill material dramatically enhances the reliability of the flip-chip devices as compared to the non-underfilled devices. Current underfills are mainly epoxy-based materials that are not reworkable after curing, which places an obstacle in Flip-Chip on Board (FCOB) technology developments. Thermally reworkable underfill is not only the key material to address the non-reworkability of the FCOB packages, but it can also be used to enhance the board-level reliability of ball grid array (BGA) and chip scale package (CSP) devices without losing their good reworkability feature. In this work, three approaches for developing thermally reworkable underfills including syntheses of thermally degradable epoxies, incorporation of special additives into standard epoxy matrix, and utilization of thermoplastic-thermoset copolymers/blends are studied. Based on these studies, reworkable underfills are then developed. Reworkable underfills developed in-house and from commercial sources are then evaluated for their reworkability and reliability to the encapsulation of FCOB, BGA, and CSP. To begin with, various thermal degradable epoxies containing carbonate or carbamate linkdage are synthesized and characterized. Among them, two diepoxides that decompose around solder reflow temperature and have good overall properties are selected and formulated into reworkable underfills for conventional capillary-flow underfilling process. A group of additives named chemical blowing agents are identified to have the capability to make the epoxy removable under certain conditions when they are incorporated into a standard epoxy matrix. Interactions between the additives and the typical epoxy formulation are thoroughly studied for the purpose of identifying good additives that provide

  17. Modeling menopause: The utility of rodents in translational behavioral endocrinology research.

    PubMed

    Koebele, Stephanie V; Bimonte-Nelson, Heather A

    2016-05-01

    The human menopause transition and aging are each associated with an increase in a variety of health risk factors including, but not limited to, cardiovascular disease, osteoporosis, cancer, diabetes, stroke, sexual dysfunction, affective disorders, sleep disturbances, and cognitive decline. It is challenging to systematically evaluate the biological underpinnings associated with the menopause transition in the human population. For this reason, rodent models have been invaluable tools for studying the impact of gonadal hormone fluctuations and eventual decline on a variety of body systems. While it is essential to keep in mind that some of the mechanisms associated with aging and the transition into a reproductively senescent state can differ when translating from one species to another, animal models provide researchers with opportunities to gain a fundamental understanding of the key elements underlying reproduction and aging processes, paving the way to explore novel pathways for intervention associated with known health risks. Here, we discuss the utility of several rodent models used in the laboratory for translational menopause research, examining the benefits and drawbacks in helping us to better understand aging and the menopause transition in women. The rodent models discussed are ovary-intact, ovariectomy, and 4-vinylcylohexene diepoxide for the menopause transition. We then describe how these models may be implemented in the laboratory, particularly in the context of cognition. Ultimately, we aim to use these animal models to elucidate novel perspectives and interventions for maintaining a high quality of life in women, and to potentially prevent or postpone the onset of negative health consequences associated with these significant life changes during aging.

  18. 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

  19. Activation of Prodrug Treosulfan at pH 7.4 and 37°C Accompanied by Hydrolysis of Its Active Epoxides: Kinetic Studies with Clinical Relevance.

    PubMed

    Romański, Michał; Urbaniak, Bartosz; Kokot, Zenon; Główka, Franciszek K

    2015-12-01

    Treosulfan (TREO), originally registered for treatment of ovarian cancer, is currently being investigated for conditioning prior to hematopoietic stem cell transplantation. TREO is a prodrug, which undergoes a pH- and temperature-dependent two-step conversion to active monoepoxide [S,S-EBDM, (2S,3S)-1,2-epoxybutane-3,4-diol-4-methanesulfonate] and diepoxide [S,S-DEB, (2S,3S)-1,2:3,4-diepoxybutane]. In this paper, the kinetics of the nonenzymatic transformation of TREO at pH 7.4 and 37°C were studied for the first time including the effects of the TREO concentration, buffer concentration, ionic strength, and the presence of NaCl. Transformation of TREO was well described by a kinetic model, which included first-order reactions for TREO activation, that is, TREO → S,S-EBDM → S,S-DEB, and pseudo-first-order reactions for the hydrolytic decomposition of S,S-EBDM and S,S-DEB. In contrast to the two-step activation of TREO, the hydrolysis of epoxides was influenced by electrolytes. In phosphate-buffered saline, decomposition of S,S-EBDM and S,S-DEB (mean half-lives 25.7 and 15.4 h) proceeded much slower than their formation (mean half-lives 1.5 and 3.5 h). In conclusion, the kinetics of the nonenzymatic transformation of TREO in the presence of plasma electrolytes cannot contribute to the very low levels of S,S-EBDM and S,S-DEB observed in patient plasma. The results also indicate that elimination of TREO proceeds primarily via conversion to S,S-EBDM.

  20. Redistribution of NMDA Receptors in Estrogen-Receptor-β-Containing Paraventricular Hypothalamic Neurons following Slow-Pressor Angiotensin II Hypertension in Female Mice with Accelerated Ovarian Failure

    PubMed Central

    Marques-Lopes, Jose; Tesfaye, Ephrath; Israilov, Sigal; Van Kempen, Tracey A.; Wang, Gang; Glass, Michael J.; Pickel, Virginia M.; Iadecola, Costantino; Waters, Elizabeth M.; Milner, Teresa A.

    2017-01-01

    Hypertension in male and aging female rodents is associated with glutamate-dependent plasticity in the hypothalamus, but existing models have failed to capture distinct transitional menopausal phases that could have a significant impact on the synaptic plasticity and emergent hypertension. In rodents, accelerated ovarian failure (AOF) induced by systemic injection of 4-vinylcyclohexane diepoxide mimics the estrogen fluctuations seen in human menopause including the perimenopause transition (peri-AOF) and postmenopause (post-AOF). Thus, we used the mouse AOF model to determine the impact of slow-pressor angiotensin II (AngII) administration on blood pressure and on the subcellular distribution of obligatory N-methyl-D-aspartate (NMDA) receptor GluN1 subunits in the paraventricular hypothalamic nucleus (PVN), a key estrogen-responsive cardiovascular regulatory area. Estrogen-sensitive neuronal profiles were identified in mice expressing enhanced green fluorescent protein under the promoter for estrogen receptor (ER) β, a major ER in the PVN. Slow-pressor AngII increased arterial blood pressure in mice at peri- and post-AOF time points. In control oil-injected (nonhypertensive) mice, AngII decreased the total number of GluN1 in ERβ-containing PVN dendrites. In contrast, AngII resulted in a reapportionment of GluN1 from the cytoplasm to the plasma membrane of ERβ-containing PVN dendrites in peri-AOF mice. Moreover, in post-AOF mice, AngII increased total GluN1, dendritic size and radical production in ERβ-containing neurons. These results indicate that unique patterns of hypothalamic glutamate receptor plasticity and dendritic structure accompany the elevated blood pressure in peri- and post-AOF time points. Our findings suggest the possibility that distinct neurobiological processes are associated with the increased blood pressure during perimenopausal and postmenopausal periods. PMID:27078860

  1. 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.

  2. 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

  3. The CU mobile Solar Occultation Flux instrument: structure functions and emission rates of NH3, NO2 and C2H6

    NASA Astrophysics Data System (ADS)

    Kille, Natalie; Baidar, Sunil; Handley, Philip; Ortega, Ivan; Sinreich, Roman; Cooper, Owen R.; Hase, Frank; Hannigan, James W.; Pfister, Gabriele; Volkamer, Rainer

    2017-02-01

    We describe the University of Colorado mobile Solar Occultation Flux instrument (CU mobile SOF). The instrument consists of a digital mobile solar tracker that is coupled to a Fourier transform spectrometer (FTS) of 0.5 cm-1 resolution and a UV-visible spectrometer (UV-vis) of 0.55 nm resolution. The instrument is used to simultaneously measure the absorption of ammonia (NH3), ethane (C2H6) and nitrogen dioxide (NO2) along the direct solar beam from a moving laboratory. These direct-sun observations provide high photon flux and enable measurements of vertical column densities (VCDs) with geometric air mass factors, high temporal resolution of 2 s and spatial resolution of 5-19 m. It is shown that the instrument line shape (ILS) of the FTS is independent of the azimuth and elevation angle pointing of the solar tracker. Further, collocated measurements next to a high-resolution FTS at the National Center for Atmospheric Research (HR-NCAR-FTS) show that the CU mobile SOF measurements of NH3 and C2H6 are precise and accurate; the VCD error at high signal to noise ratio is 2-7 %. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) from 21 July to 3 September 2014 in Colorado, the CU mobile SOF instrument measured median (minimum, maximum) VCDs of 4.3 (0.5, 45) × 1016 molecules cm-2 NH3, 0.30 (0.06, 2.23) × 1016 molecules cm-2 NO2 and 3.5 (1.5, 7.7) × 1016 molecules cm-2 C2H6. All gases were detected in larger 95 % of the spectra recorded in urban, semi-polluted rural and remote rural areas of the Colorado Front Range. We calculate structure functions based on VCDs, which describe the variability of a gas column over distance, and find the largest variability for NH3. The structure functions suggest that currently available satellites resolve about 10 % of the observed NH3 and NO2 VCD variability in the study area. We further quantify the trace gas emission fluxes of NH3 and C2H6 and production rates of NO2 from concentrated animal feeding

  4. 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

  5. Automated surveillance to detect post-procedure safety signals of approved medical devices

    PubMed Central

    Resnic, Frederic S.; Gross, Thomas P.; Marinac-Dabic, Danica; Loyo-Berrios, Nilsa; Donnelly, Sharon; Normand, Sharon-Lise T.; Matheny, Michael E.

    2016-01-01

    Context Assuring the safety of medical devices challenges current surveillance approaches which rely heavily on voluntary reporting of adverse events. Automated surveillance of clinical registries may provide early warnings in the post-market evaluation of medical device safety. Objective To determine whether automated safety surveillance of clinical registries using a computerized tool can provide early warnings regarding the safety of new cardiovascular devices. Design Prospective propensity matched cohort analysis of seven newly introduced cardiovascular devices, utilizing data from patients undergoing percutaneous coronary intervention (PCI) in Massachusetts between April 2003 and October 2007. Setting and Patients All adults undergoing PCI in Massachusetts licensed hospitals utilizing clinical data captured in the Massachusetts implementation of the National Cardiovascular Data Repository CathPCI Registry. Main Outcome Measure The presence of any safety alert, triggered if the cumulative observed risk for a given device exceeded the upper 95% confidence interval (CI) of comparator control device. Predefined sensitivity analyses assessed robustness of alerts when triggered. Results We evaluated 74,427 consecutive interventional coronary procedures. Three of 21 safety analyses triggered sustained alerts in two implantable devices. Patients receiving Taxus Express2® drug eluting stents (DES) experienced a 1.28 fold (2.87% versus 2.25%, absolute risk increase of 0.62%, CI: 0.25-0.99%) increased risk of post-procedural myocardial infarction and a 1.21 fold increase major adverse cardiac events relative to alternative DES (4.24% vs. 3.50%, absolute increase of 0.74%, CI: 0.29-1.19%). Patients receiving the Angio-Seal STS® vascular closure device (VCD) experienced a 1.51 fold increased risk (1.09% vs. 0.72%, absolute increased risk 0.37%, CI: 0.03-0.71%) increased risk of major vascular complications compared with alternative VCD. Sensitivity analyses confirmed

  6. Critical analysis of anatomical landmarks within the sphenoid sinus for transsphenoidal surgery.

    PubMed

    Ahmadipour, Yahya; Lemonas, Elias; Maslehaty, Homajoun; Goericke, Sophia; Stuck, Boris A; El Hindy, Nicolai; Sure, Ulrich; Mueller, Oliver

    2016-11-01

    The transsphenoidal approach to the sellar region has been introduced more than a 100 years ago. It is the accepted standard operative corridor to pathologies of the pituitary gland and surrounding structures. There are anatomical landmarks within the sphenoid sinus that are used for orientation directing to the sella floor or the cavernous sinus. Yet, little data can be found on the consistency of these landmarks. It is the aim of this study to evaluate the reliability of these anatomical landmarks for the surgeon's orientation. A total of 245 computed tomography (CT) volume data sets of the cranium performed according to a standardized protocol were analyzed for study purposes. CT scans of the cranium of 125 patients admitted to the emergency room of our hospital receiving a trauma spiral according to the local protocol were employed as a control group when no pathology in the sellar region was observed. In addition, preoperative CT scans of a group of 120 patients diagnosed with pituitary adenomas between 2009 and 2013 were analyzed. Image analysis of the anatomical landmarks included the minimal intercarotid distance (ICD), diameter of the sphenoid sinus (DSS), direction of the septum sinuum sphenoidalium (SSS), and the distance between vomer and clivus (VCD). The overall mean ICD was 16.2 mm, with patients suffering from adenomas showing a mean ICD of 15.8 mm compared with an average 16.5 mm in the control group. DSS was equal for both groups (adenoma group: mean 31.5 mm; controls: mean 31.3 mm). Mean VCD was 27.9 mm in patients with pituitary adenomas compared with 26.7 mm in controls. A septum of the sphenoid sinus located in the midline was found in overall 23 % only. SSS was directed into the bony shield of the internal carotid artery in 28 % of underlying tumors and in 37 % of the control group. This is the first detailed description of landmarks of the sphenoid sinus based on a large radiologic-anatomical analysis of CT scans yielding a wide

  7. Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

    PubMed

    Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

    2017-03-03

    The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical

  8. Extended Friedberg-Lee hidden symmetries, quark masses, and CP violation with four generations

    NASA Astrophysics Data System (ADS)

    Bar-Shalom, Shaouly; Oaknin, David; Soni, Amarjit

    2009-07-01

    Motivated in part by the several observed anomalies involving CP asymmetries of B and Bs decays, we consider the standard model with a 4th sequential family (SM4) which seems to offer a rather simple resolution. We initially assume T-invariance by taking the up and down-quark 4×4 mass matrix to be real. Following Friedberg and Lee (FL), we then impose a hidden symmetry on the unobserved (hidden) up and down-quark SU(2) states. The hidden symmetry for four generations ensures the existence of two zero-mass eigenstates, which we take to be the (u,c) and (d,s) states in the up and down-quark sectors, respectively. Then, we simultaneously break T-invariance and the hidden symmetry by introducing two phase factors in each sector. This breaking mechanism generates the small quark masses mu, mc and md, ms, which, along with the orientation of the hidden symmetry, determine the size of CP-violation in the SM4. For illustration we choose a specific physical picture for the hidden symmetry and the breaking mechanism that reproduces the observed quark masses, mixing angles and CP-violation, and at the same time allows us to further obtain very interesting relations/predictions for the mixing angles of t and t'. For example, with this choice we get Vtd˜(Vcb/Vcd-Vts/Vus)+O(λ2) and Vt'b˜Vt'd·(Vcb/Vcd), Vtb'˜Vt'd·(Vts/Vus), implying that Vt'd>Vt'b, Vtb'. We furthermore find that the Cabibbo angle is related to the orientation of the hidden symmetry and that the key CP-violating quantity of our model at high energies, JSM4≡Im(VtbVt'b⋆Vt'b'Vtb'⋆), which is the high-energy analogue of the Jarlskog invariant of the SM, is proportional to the light-quark masses and the measured Cabibbo-Kobayashi-Maskawa quark-mixing matrix angles: |JSM4|˜A3λ5×(mu/mt+mc/mt'-md/mb+ms/mb')˜10-5, where Ã0.81 and λ=0.2257 are the Wolfenstein parameters. Other choices for the orientation of the hidden symmetry and/or the breaking mechanism may lead to different physical outcomes. A

  9. 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

  10. Remote sensing of volcanic CO2, HF, HCl, SO2, and BrO in the downwind plume of Mt. Etna

    NASA Astrophysics Data System (ADS)

    Butz, André; Solvejg Dinger, Anna; Bobrowski, Nicole; Kostinek, Julian; Fieber, Lukas; Fischerkeller, Constanze; Giuffrida, Giovanni Bruno; Hase, Frank; Klappenbach, Friedrich; Kuhn, Jonas; Lübcke, Peter; Tirpitz, Lukas; Tu, Qiansi

    2017-01-01

    Remote sensing of the gaseous composition of non-eruptive, passively degassing volcanic plumes can be a tool to gain insight into volcano interior processes. Here, we report on a field study in September 2015 that demonstrates the feasibility of remotely measuring the volcanic enhancements of carbon dioxide (CO2), hydrogen fluoride (HF), hydrogen chloride (HCl), sulfur dioxide (SO2), and bromine monoxide (BrO) in the downwind plume of Mt. Etna using portable and rugged spectroscopic instrumentation. To this end, we operated the Fourier transform spectrometer EM27/SUN for the shortwave-infrared (SWIR) spectral range together with a co-mounted UV spectrometer on a mobile platform in direct-sun view at 5 to 10 km distance from the summit craters. The 3 days reported here cover several plume traverses and a sunrise measurement. For all days, intra-plume HF, HCl, SO2, and BrO vertical column densities (VCDs) were reliably measured exceeding 5 × 1016, 2 × 1017, 5 × 1017, and 1 × 1014 molec cm-2, with an estimated precision of 2.2 × 1015, 1.3 × 1016, 3.6 × 1016, and 1.3 × 1013 molec cm-2, respectively. Given that CO2, unlike the other measured gases, has a large and well-mixed atmospheric background, derivation of volcanic CO2 VCD enhancements (ΔCO2) required compensating for changes in altitude of the observing platform and for background concentration variability. The first challenge was met by simultaneously measuring the overhead oxygen (O2) columns and assuming covariation of O2 and CO2 with altitude. The atmospheric CO2 background was found by identifying background soundings via the co-emitted volcanic gases. The inferred ΔCO2 occasionally exceeded 2 × 1019 molec cm-2 with an estimated precision of 3.7 × 1018 molec cm-2 given typical atmospheric background VCDs of 7 to 8 × 1021 molec cm-2. While the correlations of ΔCO2 with the other measured volcanic gases confirm the detection of volcanic CO2 enhancements, correlations were found of variable

  11. 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.

  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. 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

  14. In vivo metabolism of butadiene by mice and rats: a comparison of physiological model predictions and experimental data.

    PubMed

    Medinsky, M A; Leavens, T L; Csanády, G A; Gargas, M L; Bond, J A

    1994-07-01

    1,3-Butadiene (BD), a rodent carcinogen, is metabolized to mutagenic and potentially DNA-reactive epoxides, including butadiene monoepoxide (BMO) and butadiene diepoxide. A physiological model containing five tissue groups (liver, lung, fat, slowly perfused tissues and rapidly perfused tissues) and blood was developed to describe uptake and metabolism of inhaled BD and BMO. Maximal rates for hepatic and pulmonary metabolism of BD and hepatic metabolism of BMO incorporated into the model were extrapolated from in vitro data (Csanády et al., Carcinogenesis, 13, 1143-1153, 1992). Apparent enzyme affinities used in the model were identified to the values measured in vitro. Model stimulations for BD and BMO uptake were compared to results from experiments in which groups of male Sprague-Dawley rats and B6C3F1 mice were exposed to initial concentrations of 50-5000 p.p.m. BD in closed chamber experiments and published data on BMO uptake by rats and mice. Metabolic rate constants extrapolated from in vitro data stimulated both BMO and BD uptake from closed chambers. The Vmax for hepatic metabolism of BD extrapolated from in vitro studies was 62 mumol/kg/h for rats and 340 mumol/kg/h for mice, while the Vmax for pulmonary metabolism of BD was 1.0 and 22 for rats and mice, respectively. These results demonstrate the usefulness of data derived in vitro for predicting in vivo behavior. Model simulations were also conducted in which only hepatic metabolism of BD was incorporated. These simulations underestimated BD uptake for mice, but not rats. Inclusion of in vitro-derived rates of pulmonary metabolism of BD into the model improved the fit to the data for mice. Since mice, but not rats, develop lung tumors after exposure to BD, these results point to the need for further characterize the metabolic capacity and target cells in the lung for BD and its metabolites. Once characterized, these models can be extended to predict in vivo behavior of BD in humans.

  15. AFOSR Technical Summaries.

    DTIC Science & Technology

    1988-03-01

    4J 4 -> 0 4 0- C) ’-einLOLLW >- - D - tD I a --NW 0.0M4’ (L1. L 0 ".M .- -. 10.00M. C 00. 04𔃺 V 20 - U 4 (D 4C ’a D W31.0 0 W MWC4’W -4C EW 0C 4j- U00...0Z --Lo 4A :3 WU IW ta 3 M j - 3- , * U.I(A - )13 M- L +1- Ř tD - 40- CC- - >0. 0 V)@CD4 -J 00.4 O -00M .5 3C4 .C -4 V3 Mo j -4 CL4< 0 004< 2 I Z...EOC Z L0) >, 0 -J L. -- M(D .J L Q ) tD W 3 t3C’) M M f ) 4L IA-EN- u) u - - 0.0 ᝲ. a 40r. U--InA- 4 CL -C c z 1. C 0U) I--a0. r-L CC) M ’C ) 3E WC

  16. Effect of plastic deformation on the optical and electrical properties in Cd0.96Zn0.04Te single crystals

    NASA Astrophysics Data System (ADS)

    Lmai, F.; Moubah, R.; Amiri, A. El.; Boudali, A.; Hlil, E. K.; Lassri, H.

    2017-01-01

    Using UV-visible, photoluminescence, electrical measurements and ab-initio calculations, we study the effect of introduced dislocations on the optical and electrical properties in Cd0.96Zn0.04Te crystals. To generate dislocations, a plastic deformation on the Cd(111) and Te (1 bar 1 bar 1 bar) faces was induced. It is shown that the plastic deformation results in: i) a decrease in Zn concentration in the deformed regions, which is higher on the Cd face, ii) decrease in the band gap energy, iii) an increase of acceptor concentration, and iv) the leakage current is higher on the Te face. Calculation of barrier height has led to identify the dominant defect, which is the complex Cd vacancies, acceptor center [VCd, ACd] on the Cd face and VTe on the Te side, respectively. Electronic structure calculations based on full potential linearized augmented plane waves (FPLAPW) method were performed as well and have shown that the optical band gap energy decrease upon deformation can be understood by the decrease in Zn content in the deformed regions.

  17. CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses.

    PubMed

    Covington, Cody L; Polavarapu, Prasad L

    2017-04-12

    The program CDSpecTech was developed to facilitate the analysis of chiroptical spectra, which include the following: vibrational circular dichroism (VCD) and corresponding vibrational absorption (VA) spectra; vibrational Raman optical activity (VROA) and corresponding vibrational Raman spectra; electronic circular dichroism (ECD) and corresponding electronic absorption (EA) spectra. In addition, the program allows for generating optical rotatory dispersion (ORD) as the Kramers-Kronig transform of ECD spectra. The simulation of theoretical spectra from transition strengths can be achieved using different bandshape profiles. The experimental and simulated theoretical spectra can be visually compared by displaying them together. A unique feature of CDSpecTech is performing spectral analysis using the ratio spectra; i.e., the dimensionless dissymmetry factor (DF) spectrum, which is the ratio of CD to absorption spectra, and the dimensionless circular intensity difference (CID) spectrum, which is the ratio of VROA to vibrational Raman spectra. The quantitative agreement between experimental and simulated theoretical spectra can also be assessed from the numerical similarity overlap between them. Two different similarity overlap methods are available. The program uses a graphical user interface which allows for ease of use and facilitates the analysis. All these features make CDSpecTech a valuable tool for the analysis of chiroptical spectra. The program is freely available on the World Wide Web.

  18. 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.

  19. 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.

  20. NO2 Vertical Column Density at the Marambio Antarctic Station as Retrieved by DOAS

    NASA Astrophysics Data System (ADS)

    Raponi, Marcelo M.; Jiménez, Rodrigo; Tocho, Jorge O.; Quel, Eduardo J.

    2009-03-01

    A number of chemical species present in the stratosphere in very small concentrations (parts per billion and even smaller) contribute significantly to its chemical balance. One of the main stratospheric trace gases is nitrogen dioxide (NO2). This species acts as a restrictive agent for stratospheric ozone destruction (due to the chlorine monoxide), hence the importance of its study. We present a preliminary analysis of passive remote sensing measurements carry out at the Marambio Argentinean Antarctic Base (64.233° S; 56.616° W; 197 m amsl) during the months of January—February of 2008. The spectroscopy system consists of an optical fiber (400 μm core diameter and 6 m of longitude) and a portable spectral analyzer (spectrometer HR4000, Ocean Optics). The device analyzes diffuse solar spectral irradiance in the UV-visible range (290-650 nm), collected and transferred by a zenith-pointing optical fiber. The NO2 vertical column density (VCD) is derived from the radiance spectra using the DOAS (Differential Optical Absorption Spectroscopy) technique. The system and technique allow for simultaneous measurements of different species of interest on a variety of meteorological conditions. The vertical columns obtained are compared with co-located measurements performed with EVA, a visible absorption spectrometer operated by the Instituto Nacional de Técnica Aeroespacial (INTA), Spain.

  1. Remote sensing of stratospheric O3 and NO2 using a portable and compact DOAS spectrometer

    NASA Astrophysics Data System (ADS)

    Raponi, M. M.; Jiménez, R.; Wolfram, E.; Tocho, J. O.; Quel, E. J.

    2011-01-01

    The use of passive and active remote sensing systems has largely contributed to advance our understanding of important atmospheric phenomena. Here we present a compact and portable passive DOAS (Differential Optical Absorption Spectroscopy) system, developed for measuring the vertical column density (VCD) of multiple atmospheric trace gases. We highlight the main characteristics of the system components: a mini-spectrometer (HR4000, Ocean Optics), two optical fibers (400 μm of core, 6 m and 25 cm of longitude), an external shutter and the control/data processing software. Nitrogen dioxide (NO2) and ozone (O3) VCDs are derived from solar spectra acquired during twilights (87° - 91° zenithal angles) using the DOAS technique. The analysis is carried out by solving the Beer-Lambert-Bouger (BLB) law for the main atmospheric absorbers at selected wavelength ranges. The algorithm minimizes the fitting residuals to the BLB law, having as unknown the slant column density (SCD) of the species to determine. We present measurements carried out at the Marambio Antarctic Base (64° 14' 25'' S; 56° 37' 21'' W, 197 m asl) during January - February 2008. In addition, we compare our results with co-located measurements performed with EVA, a visible absorption spectrometer of Instituto Nacional de Técnica Aeroespacial (INTA, Spain), a Dobson spectrophotometer of Servicio Meteorológico Nacional (SMN, Argentine) and the Ozone Monitoring Instrument (OMI), on board AURA satellite.

  2. 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.

  3. Analytical and preparative enantioseparation and main chiroptical properties of Iridium(III) bis(4,6-difluorophenylpyridinato)picolinato.

    PubMed

    Citti, Cinzia; Battisti, Umberto M; Ciccarella, Giuseppe; Maiorano, Vincenzo; Gigli, Giuseppe; Abbate, Sergio; Mazzeo, Giuseppe; Castiglioni, Ettore; Longhi, Giovanna; Cannazza, Giuseppe

    2016-10-07

    Almost all Iridium(III) complexes employed both as dopants in PhOLEDs and as pharmaceuticals and fluorescence bioprobes are racemic mixtures. In this study the single enantiomers of the most stable diastereomeric form fac-trans-N-N, bis[2-(4,6-difluorophenyl)pyridinato-C(2),N](picolinato)iridium(III) (FIrpic) were separated and analysed. The data obtained showed that the complex can be separated into stable optically active Λ and Δ isomers employing cellulose based chiral stationary phase both in normal and polar phase mode. Their chirality was confirmed and their absolute configuration assigned employing several methods (DFT and TDDFT calculations, CD and VCD). The CPL spectroscopy of the isolated enantiomers of FIrpic was also recorded due to its possible value in the OLEDs field. The chromatographic method was applied for a semipreparative purpose demonstrating that polar organic solvent chromatography (POSC) could be used to avoid the low-solubility issues associated with these Iridium(III) complexes. Finally, the chemical and stereochemical stability of the single isomers was evaluated under thermal stress by liquid chromatography coupled to high-resolution mass spectrometry (LC-QTOF) on both chiral and achiral columns. No racemization and/or isomerization was observed; however, the dissociation of the ancillary ligand was demonstrated employing LC-QTOF.

  4. Investigation of point defects and electrical properties of the In-doped CdMnTe grown by traveling heater method

    NASA Astrophysics Data System (ADS)

    Wen, Xuliang; Zhang, Jijun; Mao, Yifei; Min, Jiahua; Liang, Xiaoyan; Huang, Jian; Tang, Ke; Wang, Linjun

    2017-04-01

    The In-doped Cd0.9Mn0.1Te (CdMnTe:In) crystal was grown by the Travelling Heater Method. The crystallity of the CdMnTe:In wafers extracted from different part of the CdMnTe:In ingot was studied including the impurity contents, the Te inclusions and the Mn composition. The point defects in the CdMnTe:In wafers were revealed by the Photo-Induced Current Transient Spectroscopy (PICTS). The ionization energy, the capture cross-section and the concentration of the defect traps in different parts of the ingot were identified. The PICTS result showed the concentration of the VCd decreases from the top part to the tail part along the bulk while the concentration of A-center increase. The wafers from the middle part of the bulk were proved to have less deep level point defects compared to other parts of the crystal bulk, and had higher electronic performance with the resistivity up to 3.07 × 1010 Ω cm and the μτ value up to 1.45 × 10-3 cm2 V-1. The concentration of the deep level point defects plays an important role in the electrical properties, especially for the mobility-lifetime product.

  5. 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.

  6. 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.

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

    NASA Technical Reports Server (NTRS)

    Callahan, Michael R.; Sargusingh, Miriam J.

    2015-01-01

    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. Its rotating cascading distiller operates similarly to the state of the art (SOA) vapor compressor distiller (VCD), but its control scheme and ancillary components are judged to be straightforward and simpler to implement into a successful design. 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). The key objectives for the CDS 2.0 design task is to provide a flight forward ground prototype that demonstrates improvements over the SOA system in the areas of increased reliability and robustness, and reduced mass, power and volume. It will also incorporate exploration-class automation. The products of this task are a preliminary flight system design and a high fidelity prototype of an exploration class CDS. These products will inform the design and development of the third generation CDS which is targeted for on-orbit DTO. This paper details the preliminary design of the CDS 2.0.

  8. 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.

  9. 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.

  10. First-principles DFT+GW study of oxygen doped CdTe

    NASA Astrophysics Data System (ADS)

    Orellana, Walter; Flores, Mauricio A.; Menéndez-Proupin, Eduardo

    The role of oxygen doping in CdTe is addressed by first-principles calculations. Formation energies, charge transition levels and quasiparticle defect states are calculated within the DFT+GW formalism. The formation of a new defect is identified, the (OTe -TeCd) complex. This complex is energetically favored over both isovalent (OTe) and interstitial oxygen (Oi). We find that incorporation of oxygen passivates the harmful deep energy levels derived from Te antisites, suggesting an improvement in the efficiency of CdTe based solar cells. Our calculations indicate that both (OTe) and (Oi) have low formation energies. Moreover, (OCd) is only stable in the neutral charge state and undergoes a Jahn-Teller distortion. The (VCd - OTe) complex is found to be a shallow acceptor with a high formation energy. We also report an oxygen-related interstitial defect, which plays a key role in the diffusion mechanism of oxygen in CdTe. Support by FONDECYT Grant No. 1130437 is acknowledged. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02).

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

    PubMed

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

    2016-09-09

    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.

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

    PubMed Central

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

    2015-01-01

    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. PMID:26349075

  13. 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.

  14. Kinetic Model of Decarburization and Denitrogenation in Vacuum Oxygen Decarburization Process for Ferritic Stainless Steel

    NASA Astrophysics Data System (ADS)

    Xu, Yingtie; Chen, Zhaoping; Zhang, Ge

    2009-06-01

    The characteristics and classification of decarburization and denitrogenation in the vacuum vessel for stainless steel production are analyzed. Based on the analysis of movements of the liquid steel and bubbles, the kinetics of decarburization and denitrogenation in the vacuum oxygen decarburization (VOD) process has been studied. A kinetic model of decarburization and denitrogenation has been developed to simulate the VOD process, considering each reaction zone as oxygen blowing crater, bottom blowing plume, steel/slag interface, and plume eye. As a result, it is possible to quantify the contribution of each reaction zone in decarburization and denitrogenation rate at a different stage in the VOD process. Specific trials at a vacuum induction furnace were performed to refine stainless steel in vacuum carbon deoxidation (VCD) and VOD style, respectively. The trial results are in good agreement with the model calculation. Combining the trials and the model calculation and the influence of temperature control, critical carbon content selection on the terminal total [C] + [N] content can be discussed further to provide a reasonable proposal for high-quality ferritic stainless steel production.

  15. Estimation of NOx emissions from Delhi using Car MAX-DOAS observations and comparison with OMI satellite data

    NASA Astrophysics Data System (ADS)

    Shaiganfar, R.; Beirle, S.; Sharma, M.; Chauhan, A.; Singh, R. P.; Wagner, T.

    2011-11-01

    We present the first Multi-Axis-(MAX-) DOAS observations in India performed during April 2010 and January 2011 in Delhi and nearby regions. The MAX-DOAS instrument was mounted on a car roof, which allowed us to perform measurements along individual driving routes. From car MAX-DOAS observations along closed circles around Delhi, together with information on wind speed and direction, the NOx emissions from the greater Delhi area were determined: our estimate of 4.4 × 1025 molecules s-1 is found to be slightly lower than the corresponding emission estimates using the EDGAR emission inventory and substantially smaller compared to a recent study by Gurjar et al. (2004). We also determined NOx emissions from Delhi using OMI satellite observations on the same days. These emissions are slightly smaller than those from the car MAX-DOAS measurements. Finally the car MAX-DOAS observations were also used for the validation of simultaneous OMI satellite measurements of the tropospheric NO2 VCD and found a good agreement of the spatial patterns. Concerning the absolute values, OMI data are, on average, higher than the car MAX-DOAS observations close to strong emission sources, and vice versa over less polluted regions. Our results indicate that OMI NO2 VCDs are biased low over strongly polluted regions, probably caused by inadequate a-priori profiles used in the OMI satellite retrieval.

  16. Estimation of NOx emissions from Delhi using car MAX-DOAS observations and comparison with OMI satellite data

    NASA Astrophysics Data System (ADS)

    Shaiganfar, R.; Beirle, S.; Sharma, M.; Chauhan, A.; Singh, R. P.; Wagner, T.

    2011-07-01

    We present the first Multi-Axis- (MAX-) DOAS observations in India performed during April 2010 and January 2011 in Delhi and nearby regions. The MAX-DOAS instrument was mounted on a car roof, which allowed us to perform measurements along individual driving routes. From car MAX-DOAS observations along closed circles around Delhi, together with information on wind speed and direction, the NOx emissions from the greater Delhi area were determined: our estimate of 3.7 × 1025 molec s-1 is found to be slightly lower than the corresponding emission estimates using the EDGAR data base and substantially smaller compared to a recent study by Gurjar et al. (2004). We have also used the MAX-DOAS observations of the tropospheric NO2 VCD for validation of simultaneous satellite observations from the OMI instrument and found a good agreement of the spatial patterns. The absolute values show a reasonably good agreement. However, OMI data tends to underestimate the tropospheric NO2 VCDs in regions with high pollution levels, and tends to overestimate the tropospheric NO2 VCDs in more clean areas. These findings indicate possible discrepancies between the true vertical NO2 profiles and the profile assumptions in the OMI satellite retrieval.

  17. A script for automated 3-dimentional structure generation and conformer search from 2- dimentional chemical drawing.

    PubMed

    Ishikawa, Yoshinobu

    2013-01-01

    Building 3-dimensional (3D) molecules is the starting point in molecular modeling. Conformer search and identification of a global energy minimum structure are often performed computationally during spectral analysis of data from NMR, IR, and VCD or during rational drug design through ligand-based, structure-based, and QSAR approaches. I herein report a convenient script that allows for automated building of 3D structures and conformer searching from 2-dimensional (2D) drawing of chemical structures. With this Bash shell script, which runs on Mac OS X and the Linux platform, the tasks are consecutively and iteratively executed without a 3D molecule builder via the command line interface of the free (academic) software OpenBabel, Balloon, and MOPAC2012. A large number of 2D chemical drawing files can be processed simultaneously, and the script functions with stereoisomers. Semi-empirical quantum chemical calculation ensures reliable ranking of the generated conformers on the basis of energy. In addition to an energy-sorted list of file names of the conformers, their Gaussian input files are provided for ab initio and density functional theory calculations to predict rigorous electronic energies, structures, and properties. This script is freely available to all scientists.

  18. 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.

  19. 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.

  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. 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.

  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. 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.

  4. Study of solar variability impact on nitrogen dioxide: 2004-2013

    NASA Astrophysics Data System (ADS)

    Constantin, Daniel-Eduard; Voiculescu, Mirela; Merlaud, Alexis; Van Roozendael, Michel

    2015-04-01

    Nitrogen dioxide (NO2) locally plays an important role in the radiation budget by absorbing solar radiation at ultraviolet (UV) and visible wavelengths. The influence of solar variability on the inter-annual variability and trends in nitrogen dioxide is evaluated for a period of 10 years (2004-2013) using monthly mean tropospheric NO2 measurements of the Ozone Monitoring Instrument (OMI) version 2.0. Possible signatures of solar variability on nitrogen dioxide time series of NO2 over several cities were analyzed using various statistical methods. Various solar proxies were selected, in order to separate between possible links to solar irradiance and to solar wind. Several locations with different levels of pollution, located in different places of the world (Athens, Jungfraujoch, Lauder, Lisbon, Moscow, and Uccle), were selected. Observations show a clear 27 day period of the NO2 tropospheric Vertical Column Density (VCD) or total Slant Column Density (SCD). NO2 content decreases with increasing activity above polluted areas (e.g. Athens, Moscow) while for unpolluted areas there is no evident correlation (e.g. Lauder, Jungfraujoch). Possible effects of solar wind on NO2 content are observed as well, but the relationship is less clear, since polluted areas seem to respond differently to solar wind variations. The mechanism by which NO2 content can be affected by solar variations relate mainly to ozone production but other paths by which solar energy may be transferred to the lower atmosphere are investigated.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. New developments of a multifrequency virtual spectrometer: stereo-electronic, dynamical and environmental effects on chiroptical spectra

    PubMed Central

    Barone, Vincenzo; Baiardi, Alberto; Bloino, Julien

    2015-01-01

    Computational spectroscopy has recently evolved from a field reserved to specialists toward a general tool allowing interpretations and analyses of experimental results. However, the current practice of providing tables of transitions for rigid geometries, possibly tuned by phenomenological broadening is by far too naive. In order to improve this situation, in the last few years we have been developing a general, robust and user-friendly virtual spectrometer (VS) able to complement experimental studies for complex systems in condensed phases. The VS is based on flexible graphical pre- and post-processing tools interfaced with general number crunching software. This last tool is rooted on several electronic structure methodologies (DFT, TD-DFT, post-Hartree-Fock), powerful discrete/continuum models for describing environmental effects, and general vibrational and vibronic models. These last topics are the main focus of this work, which sketches our latest developments related to effective inclusion of anharmonic contributions, together with time-independent and/or time-dependent descriptions of vibronic transitions including Franck-Condon, Herzberg-Teller, and Duschinsky effects. Some test cases are described in some detail with the aim of showing the role of different effects in ruling vibrational (VCD) and electronic (ECD, CPL) chiral spectroscopies. PMID:24839096

  12. Effect of the total angular momentum on the dynamics of the H2 + H2 system.

    PubMed

    Garcia, Ernesto; Saracibar, Amaia; Sánchez, Carlos; Laganà, Antonio

    2009-12-31

    Extended full-dimensional quasiclassical trajectory calculations have been performed for the H(a)H(b) (v(ab) = 10, 11, 12, 13, 14, j(ab) = 0) + H(c)H(d) (v(cd) = 0, j(cd) = 0) collisions at values of the translational energy ranging from threshold to 1.5 eV and values of the total angular momentum quantum number J varying from zero to very large ones. Collision-induced dissociation, four-center exchange reaction, and single exchange process probabilities have been calculated. Full-dimensional classical calculations were found to reproduce well the corresponding (J = 0) quantum results, including the thresholds. In contrast, the agreement of full-dimensional classical calculations with the corresponding both quantum and classical reduced dimensionality ones was found to be poor. The effect of varying J on the efficiency of the various processes has also been investigated. Four-center reactions were found to be favored by low values of J, whereas dissociation processes were found to be favored by higher values of J, as expected from the fact that energy exchange takes place at longer range than mass exchange. To evaluate to what extent the J = 0 full-dimensional calculations represent the unconstrained dynamics of the system, J-shift model classical results were compared with the all-J ones. Product vibrational distributions for both partially dissociative and exchange processes were also found to depend significantly on the value of J.

  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.

  14. Enantioselective self-assembly of triangular Dy3 clusters with single-molecule magnet behavior.

    PubMed

    Lin, Shuang-Yan; Wang, Chao; Zhao, Lang; Tang, Jinkui

    2014-12-01

    Three pairs of enantiopure chiral triangular Ln3 clusters, [Ln3LRRRRRR/SSSSSS(μ3-OH)2(H2O)2(SCN)4]⋅xCH3OH⋅yH2O (R-Dy3, Ln=Dy, x=6, y=0; S-Dy3, Ln=Dy, x=6, y=1; R-Ho3, Ln=Ho, x=6, y=1; S-Ho3, Ln=Ho, x=6, y=1; R-Er3, Ln=Er, x=6, y=0; S-Er3, Ln=Er, x=6, y=1), have been successfully synthesized by a rational enantioselective synthetic strategy. The core of triangular Ln3 is bound in the central N6O3 of the macrocyclic ligand, and the coordination spheres of Ln ions are completed by four SCN(-) anions and two H2O molecules in axial positions of the macrocycle. The circular dichroism (CD) and vibrational circular dichroism (VCD) spectra of the enantiomers demonstrate that the chirality is successfully transferred from the ligands to the resulting Ln3 clusters. Ac susceptibility measurements reveal that single-molecule magnet behavior occurs for both enantiopure clusters of R-Dy3 and S-Dy3. This work is one of the few examples of the successful design of a pair of triangular Dy3 clusters showing simultaneously slow magnetic relaxation and optical activity, and this might open up new opportunities to develop novel multifunctional materials.

  15. 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.

  16. 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.

  17. 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

  18. The CU Airborne MAX-DOAS instrument: vertical profiling of aerosol extinction and trace gases

    NASA Astrophysics Data System (ADS)

    Baidar, S.; Oetjen, H.; Coburn, S.; Dix, B.; Ortega, I.; Sinreich, R.; Volkamer, R.

    2013-03-01

    The University of Colorado Airborne Multi-Axis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument uses solar stray light to detect and quantify multiple trace gases, including nitrogen dioxide (NO2), glyoxal (CHOCHO), formaldehyde (HCHO), water vapor (H2O), nitrous acid (HONO), iodine monoxide (IO), bromine monoxide (BrO), and oxygen dimers (O4) at multiple wavelengths (absorption bands at 360, 477, 577, 632 nm) simultaneously in the open atmosphere. The instrument is unique as it (1) features a motion compensation system that decouples the telescope field of view from aircraft movements in real time (<0.35° accuracy), and (2) includes measurements of solar stray light photons from nadir, zenith, and multiple elevation angles forward and below the plane by the same spectrometer/detector system. Sets of solar stray light spectra collected from nadir to zenith scans provide some vertical profile information within 2 km above and below the aircraft altitude, and the vertical column density (VCD) below the aircraft is measured in nadir view. Maximum information about vertical profiles is derived simultaneously for trace gas concentrations and aerosol extinction coefficients over similar spatial scales and with a vertical resolution of typically 250 m during aircraft ascent/descent. The instrument is described, and data from flights over California during the CalNex (California Research at the Nexus of Air Quality and Climate Change) and CARES (Carbonaceous Aerosols and Radiative Effects Study) air quality field campaigns is presented. Horizontal distributions of NO2 VCD (below the aircraft) maps are sampled with typically 1 km resolution, and show good agreement with two ground-based MAX-DOAS instruments (slope = 0.95 ± 0.09, R2 = 0.86). As a case study vertical profiles of NO2, CHOCHO, HCHO, and H2O concentrations and aerosol extinction coefficients, ɛ, at 477 nm calculated from O4 measurements from a low approach at Brackett airfield inside the

  19. 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.

  20. Facies characterization based on physical properties from downhole logging for the sediment record of Lake Van, Turkey

    NASA Astrophysics Data System (ADS)

    Baumgarten, H.; Wonik, T.; Kwiecien, O.

    2014-11-01

    Lake Van (Turkey) is the 4th largest terminal lake in the world and is located at a key position for climatic reconstruction. The ICDP project 'PALEOVAN' is a deep-drilling campaign initiated in the summer of 2010 to enhance the understanding of paleoclimatic and paleoenvironmental conditions in the Middle East for a period of 550,000 years. Multiple coring of two sites (Northern Basin and Ahlat Ridge) at a water depth of up to 360 m has been performed. The sedimentary record is mainly composed of clayey silts and tephra deposits that were supplied by four volcanic sources: 1) the Süphan volcano, located on the northern shore, 2) the Nemrut volcano, 15 km west of the westernshore, 3) the Incekaya volcano, on the southwestern shore and 4) intralake eruptive centers. The dominant chemical composition of the volcanic sources is known from studies of land deposits. High-quality downhole logs have been acquired from both sites. To construct a continuous lithological profile, 180 m of downhole logging data from the Ahlat Ridge have been analyzed by cluster analysis. To improve the differentiation of the sediments, two elemental intensity profiles from x-ray fluorescence core-scanning (calcium and zirconium) performed on the composite profile core material were added to the cluster analysis. Five cluster units were derived and transformed into three tephra and two clayey silt units. To compare the two clayey silt units with the composite profile from the visual core description (VCD) that showed 15 lithological units, the composite profile was classified into two major groups of lacustrine sediments: banded clayey silts (interpreted as glacial deposits) and laminated clayey silts (interpreted as interglacial deposits). Despite this simplification, no correlation between the two clayey silt units derived from cluster analysis and the banded and laminated clayey silts could be found. The following reasons are proposed: (a) the comparability of the datasets was limited by

  1. 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

  2. Quantum yield in blue-emitting anthracene derivatives: vibronic coupling density and transition dipole moment density.

    PubMed

    Uejima, Motoyuki; Sato, Tohru; Yokoyama, Daisuke; Tanaka, Kazuyoshi; Park, Jong-Wook

    2014-07-21

    A theoretical design principle for enhancement of the quantum yield of light-emitting molecules is desired. For the establishment of the principle, we focused on the S1 states of blue-emitting anthracene derivatives: 2-methyl-9,10-di(2'-naphthyl)anthracene (MADN), 4,9,10-bis(3',5'-diphenylphenyl)anthracene (MAM), 9-(3',5'-diphenylphenyl)-10-(3'',5''-diphenylbiphenyl-4''-yl) anthracene (MAT), and 9,10-bis(3''',5'''-diphenylbiphenyl-4'-yl) anthracene (TAT) [Kim et al., J. Mater. Chem., 2008, 18, 3376]. The vibronic coupling constants and transition dipole moments were calculated and analyzed by using the concepts of vibronic coupling density (VCD) and transition dipole moment density (TDMD), respectively. It is found that the driving force of the internal conversions and vibrational relaxations originate mainly from the anthracenylene group. On the other hand, fluorescence enhancement results from the large torsional distortion of the side groups in the S1 state. The torsional distortion is caused by the diagonal vibronic coupling for the lowest-frequency mode in the Franck-Condon (FC) S1 state, which originates from a small portion of the electron density difference on the side groups. These findings lead to the following design principles for anthracene derivatives with a high quantum yield: (1) reduction in the electron density difference and overlap density between the S0 and S1 states in the anthracenylene group to suppress vibrational relaxation and radiationless transitions, respectively; (2) increase in the overlap density in the side group to enhance the fluorescence.

  3. Effects of Vitamin C or E on the Pro-inflammatory Cytokines, Heat Shock Protein 70 and Antioxidant Status in Broiler Chicks under Summer Conditions.

    PubMed

    Jang, In-Surk; Ko, Young-Hyun; Moon, Yang-Soo; Sohn, Sea-Hwan

    2014-05-01

    The present study was carried out to investigate the effects of dietary antioxidants on pro-inflammatory cytokines, heat shock protein (HSP) and antioxidant status in broiler chicks under summer conditions. A total of 162, 3-d-old broiler chicks were randomly assigned to a basal diet (CON) and the basal diet supplemented with vitamin C (200 mg/kg diet, VCD) or vitamin E (100 mg/kg, VED) until 35 day of age. All birds were exposed to summer diurnal heat stress at average daily fluctuations of temperature between 32°C to 34°C at day to 27°C to 29°C at night for the entire feeding periods. There was no significant difference in body weight, feed to gain ratio and the relative organ weight except the thymus in response to dietary vitamin C or E supplementation. However, the mRNA expression of interleukin (IL)-1β, IL-6, interferon (IFN)-γ, Toll like receptor (TLR)-4 and HSP70 in the liver of birds fed diet containing vitamin C significantly (p<0.05) decreased compared with those in birds fed basal diet. Dietary vitamin E also showed a significant (p<0.05) decrease in the mRNA expression of IL-6 and HSP70 compared with a basal diet. Total antioxidant status (TAS) in serum of birds fed vitamin C supplemented diet was significantly (p<0.05) higher with than that in birds a basal diet. Lipid peroxidation in serum and liver resulted in a significant (p<0.05) decrease in response to dietary vitamin C or E supplementation. In conclusion, dietary supplementation with antioxidant vitamins, especially vitamin C resulted in a significant decrease in the mRNA expression of pro-inflammatory cytokines and HSP70, and higher antioxidant parameters than that of birds on the basal diet under summer conditions.

  4. 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.

  5. 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

  6. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-07

    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.

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

    PubMed

    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.

  8. Peptides as Model Systems for the Unfolded State of Proteins Explored By Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schweitzer-Stenner, Reinhard; Measey, Thomas; Hagarman, Andrew

    2008-11-01

    Unfolded proteins are generally thought to be structurally random with a minimum of non-local interactions. This concept implies that with the exception of glycine and proline the conformational propensities of amino acid residues in polypeptides should be comparable in that they all sample the statistically allowed region of the Ramachandran plot. However, over the last ten years experimental and computational evidence has emerged for the notion that the conformational space of residues might be more restricted than predicted by random or statistical coil models. We have developed several algorithms which can be used to simulate the amide I band profile of the IR, isotropic Raman, anisotropic Raman and Vibrational Circular Dichroism (VCD) spectra of polypeptides based on assumed ensembles of side chain conformations. The simulations are generally restricted by 3JcαHNH coupling constants obtained from NMR spectroscopy. A comparison with experimental results reveals that e.g. alanine has a clear preference for the so called polyproline II (PPII) conformation in short peptides. The situation becomes more complex if longer polyalanines are doped with negatively charged residues. For the so-called XAO-peptide (X2A7O2, X: diaminobutyric acid, O;ornithine) we found a more compact structure owing to multiple turn conformations sampled by the X2A7 interfaces. For Salmon Calcitonin, a 32-residue hormone, we identified a mixture of PPII, β-strand and helical conformations. Currently, we are in the process of investigating short GxG (x; different natural amino acid residues) peptides in terms of conformational distributions obtained from coil libraries. This will enable us obtain the conformational preferences of amino acid residues in the absence of nearest neighbor interactions.

  9. 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.

  10. A Survey of Volcanic Degassing in the Americas Since 2004

    NASA Astrophysics Data System (ADS)

    Carn, S. A.; Krotkov, N. A.; Krueger, A. J.; Yang, K.

    2007-05-01

    The Ozone Monitoring Instrument (OMI) on NASA's Aura satellite is the first space-based instrument providing daily measurements of sulfur dioxide (SO¬2) in the lower troposphere and boundary layer. We use these daily observations, plus monthly and annual averages of OMI SO2 data, to assess the magnitude and variability of SO2 emissions from passive volcanic degassing in the Americas since September 2004. To properly assess the magnitude of non-eruptive degassing, any signal due to drifting eruption clouds must first be removed from the long-term averages. We derive a first-order evaluation of emission strengths from the maximum value of the average SO2 vertical column density (VCD) measured close to sources. Emissions from well-known volcanic SO2 sources such as Kilauea, Popocatépetl, Masaya, Tungurahua, Láscar and Soufrière Hills are clearly identified. We also note elevated SO2 VCDs close to the remote Lastarria volcano (Chile), with an ambiguous source that could be magmatic degassing and/or combustion of preexisting sulfur deposits. Several SO2 anomalies are collocated with copper smelters in Peru and Chile, indicating significant anthropogenic SO2 emissions in this region. Measurements of SO2 emissions from Anatahan (CNMI) and Ubinas (Peru) demonstrate OMI's ability to identify and monitor episodic degassing at remote volcanoes. Detailed evaluation of relative source strengths requires accurate knowledge of the air mass factor (AMF) used in SO2 retrievals and of local dispersion processes. The AMF depends on several parameters including the SO2 vertical distribution, cloud fraction, aerosol loading, surface reflectivity, ozone column amount and satellite viewing geometry. Efforts to model and correct for the AMF dependence will be discussed. OMI measurements are an effective and economical tool for daily quantification of SO2 emissions and surveys such as could be incorporated into regularly updated assessments of global volcanic and anthropogenic SO2

  11. Eucapnic voluntary hyperpnoea and exercise-induced vocal cord dysfunction

    PubMed Central

    Turmel, Julie; Gagnon, Simon; Bernier, Mélanie; Boulet, Louis-Philippe

    2015-01-01

    Introduction Exercise-induced bronchoconstriction (EIB) is a common condition in endurance athletes. Exercise-induced vocal cord dysfunction (EIVCD) is a frequent confounder of EIB. The diagnosis of EIVCD may be challenging and can be missed as the problem is often intermittent and may only occur during intense exercise. Eucapnic voluntary hyperventilation (EVH) is the best test to detect EIB. This pilot study aimed to assess if EVH could be helpful in the diagnosis of EIVCD associated or not to EIB in athletes. Methods A nasolaryngoscopy was performed during a 6 min EVH test, in 13 female athletes suspected to have VCD, aged 21±7 years. Image analysis was conducted by two Ear Nose and Throat surgeons in random order. Results During the EVH, three athletes showed incomplete paradoxical vocal cords movement, without inspiratory stridor. However, 12 athletes showed marked supraglottic movement without inspiratory stridor. In two athletes, this supraglottic movement was severe, one showing a marked collapse of the epiglottis with an almost complete obstruction of the larynx by the arytenoid cartilage mucosa. In 3 of the 12 athletes with supraglottic movement, severe vibration of the mucosa covering the arytenoid cartilages was also observed. Conclusions EVH challenge in athletes can provide information on various types of glottic and supraglottic obstruction in reproducing laryngeal movements during hyperventilation. Our findings make us suggest that exercise induced upper airway obstructions should be named: Exercise-induced laryngeal obstruction (EILO). Then, EILO should be divided in three categories: supraglottic, glottic (EIVCD) and mixed (glottic and supraglottic) obstruction. PMID:27900141

  12. 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

  13. 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.

  14. First estimates of global free-tropospheric NO2 abundances derived using a cloud-slicing technique applied to satellite observations from the Aura Ozone Monitoring Instrument (OMI)

    NASA Astrophysics Data System (ADS)

    Choi, S.; Joiner, J.; Choi, Y.; Duncan, B. N.; Vasilkov, A.; Krotkov, N.; Bucsela, E.

    2014-10-01

    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 > 10) 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.

  15. 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.

  16. 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.

  17. 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).

  18. Evaluation of tropospheric SO2 retrieved from MAX-DOAS measurements in Xianghe, China

    NASA Astrophysics Data System (ADS)

    Wang, T.; Hendrick, F.; Wang, P.; Tang, G.; Clémer, K.; Yu, H.; Fayt, C.; Hermans, C.; Gielen, C.; Pinardi, G.; Theys, N.; Brenot, H.; Van Roozendael, M.

    2014-03-01

    Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of sulfur dioxide (SO2) have been performed at the Xianghe station (39.75° N, 116.96° E) located at ~50 km southeast of Beijing from March 2010 to February 2013. Tropospheric SO2 vertical profiles and corresponding vertical column densities (VCDs), retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations, have been used to study the seasonal and diurnal cycles of SO2, in combination to correlative measurements from in situ instruments, as well as meteorological data. A marked seasonality was observed in both SO2 VCD and surface concentration, with a maximum in winter (February) and a minimum in summer (July). This can be explained by the larger emissions in winter due to the domestic heating and more favorable meteorological conditions for the accumulation of SO2 close to the ground during this period. Wind speed and direction are also found to be two key factors in controlling the level of the SO2-related pollution at Xianghe. In the case of east or southwest wind, the SO2 concentration rises with the increase of the wind speed, since heavy polluting industries are located to the east and southwest of the station. In contrast, when wind comes from other directions, the stronger the wind, the less SO2 is observed. Regarding the diurnal cycle, the SO2 amount is larger in the early morning and late evening and lower at noon, in line with the diurnal variation of pollutant emissions and atmospheric stability. The observed diurnal cycles of MAX-DOAS SO2 surface concentration are also in very good agreement (correlation coefficient close to 0.9) with those from collocated in-situ data, demonstrating the reliability and robustness of our retrieval.

  19. Evaluation of tropospheric SO2 retrieved from MAX-DOAS measurements in Xianghe, China

    NASA Astrophysics Data System (ADS)

    Wang, Ting; Hendrick, Francois; Wang, Pucai; Tang, Guiqian; Clémer, Katrijn; Yu, Huan; Fayt, Caroline; Hermans, Christian; Gielen, Clio; Pinardi, Gaia; Theys, Nicolas; Brenot, Hugues; Van Roozendael, Michel

    2014-05-01

    Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of sulfur dioxide (SO2) have been performed at the Xianghe station (39.77°N, 117.0°E) located at ~50 km South-East of Beijing from March 2010 to February 2013. Tropospheric SO2 vertical profiles and corresponding vertical column densities (VCDs), retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations, have been used to study the seasonal and diurnal cycles of SO2, in combination to correlative measurements from in situ instruments, as well as meteorological data. A marked seasonality is observed in both SO2 VCD and surface concentration, with a maximum in winter (February) and a minimum in summer (July). This can be explained by the larger emissions in winter due to the domestic heating and more favorable meteorological conditions for the accumulation of SO2 close to the ground during this period. Wind speed and direction are also found to be two key parameters in controlling the level of the SO2-related pollution at Xianghe. In the case of east or southwest wind, the SO2 concentration rises with the increase of the wind speed, since heavy polluting industries are located to the east and southwest of the station. In contrast, when wind comes from other directions, the stronger the wind, the less SO2 is observed. Regarding the diurnal cycle, the SO2 amount is larger in the early morning and late evening and lower at noon, in line with the diurnal variation of pollutant emissions and atmospheric stability. The observed diurnal cycles of MAX-DOAS SO2 surface concentration are also in very good agreement (correlation coefficient close to 0.9) with those from collocated in-situ data, demonstrating the reliability and robustness of our retrieval.

  20. 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.

  1. Improved satellite retrievals of NO2 and SO2 over the Canadian oil sands and comparisons with surface measurements

    NASA Astrophysics Data System (ADS)

    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.

    2014-04-01

    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 >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.

  2. 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.

  3. Reconciliation of chemical, enzymatic, spectroscopic and computational data to assign the absolute configuration of the DNA base lesion spiroiminodihydantoin.

    PubMed

    Fleming, Aaron M; Orendt, Anita M; He, Yanan; Zhu, Judy; Dukor, Rina K; Burrows, Cynthia J

    2013-12-04

    The diastereomeric spiroiminodihydantoin-2'-deoxyribonucleoside (dSp) lesions resulting from 2'-deoxyguanosine (dG) or 8-oxo-7,8-dihydro-2'-deoxyguanosine (dOG) oxidation have generated much attention due to their highly mutagenic nature. Their propeller-like shape leads these molecules to display mutational profiles in vivo that are stereochemically dependent. However, there exist conflicting absolute configuration assignments arising from electronic circular dichroism (ECD) and NOESY-NMR experiments; thus, providing definitive assignments of the 3D structure of these molecules is of great interest. In the present body of work, we present data inconsistent with the reported ECD assignments for the dSp diastereomers in the nucleoside context, in which the first eluting isomer from a Hypercarb HPLC column was assigned to be the S configuration, and the second was assigned the R configuration. The following experiments were conducted: (1) determination of the diastereomer ratio of dSp products upon one-electron oxidation of dG in chiral hybrid or propeller G-quadruplexes that expose the re or si face to solvent, respectively; (2) absolute configuration analysis using vibrational circular dichroism (VCD) spectroscopy; (3) reinterpretation of the ECD experimental spectra using time-dependent density functional theory (TDDFT) with the inclusion of 12 explicit H-bonding waters around the Sp free bases; and (4) reevaluation of calculated specific rotations for the Sp enantiomers using the hydration model in the TDDFT calculations. These new insights provide a fresh look at the absolute configuration assignments of the dSp diastereomers in which the first eluting from a Hypercarb-HPLC column is (-)-(R)-dSp and the second is (+)-(S)-dSp. These assignments now provide the basis for understanding the biological significance of the stereochemical dependence of enzymes that process this form of DNA damage.

  4. 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

  5. Comparison of the biotransformation of 1,3-butadiene and its metabolite, butadiene monoepoxide, by hepatic and pulmonary tissues from humans, rats and mice.

    PubMed

    Csanády, G A; Guengerich, F P; Bond, J A

    1992-07-01

    1,3-Butadiene (BD), a widely used monomer in the production of synthetic rubber and other resins, is one of the 189 hazardous air pollutants identified in the 1990 Clean Air Act Amendments. BD induces tumors at multiple organ sites in B6C3F1 mice and Sprague-Dawley rats; mice are much more susceptible to the carcinogenic action of BD than are rats. Previous in vivo studies have indicated higher circulating blood levels of butadiene monoepoxide (BMO), a potential carcinogenic metabolite of BD, in mice compared to rats, suggesting that species differences in the metabolism of BD may be responsible for the observed differences in carcinogenic susceptibility. The metabolic fate of BD in humans is unknown. The objective of these studies was to quantitate in vitro species differences in the oxidation of BD and BMO by cytochrome P450-dependent monooxygenases and the inactivation of BMO by epoxide hydrolases and glutathione S-transferases using microsomal and cytosolic preparations of livers and lungs obtained from Sprague-Dawley rats, B6C3F1 mice and humans. Maximum rates for BD oxidation (Vmax) were highest for mouse liver microsomes (2.6 nmol/mg protein/min) compared to humans (1.2) and rats (0.6). The Vmax for BD oxidation by mouse lung microsomes was similar to that of mouse liver but greater than 10-fold higher than the Vmax for the reaction in human or rat lung microsomes. Correlation analysis revealed that P450 2E1 is the major P450 enzyme responsible for oxidation of BD to BMO. Only mouse liver microsomes displayed quantifiable rates for metabolism of BMO to butadiene diepoxide (Vmax = 0.2 nmol/mg protein/min), a known rodent carcinogen. Human liver microsomes displayed the highest rate of BMO hydrolysis by epoxide hydrolases. The Vmax in human liver microsomes ranged from 9 to 58 nmol/mg protein/min and was at least 2-fold higher than the Vmax observed in mouse and rat liver microsomes. The Vmax for glutathione S-transferase-catalyzed conjugation of BMO with

  6. Highly resolved global distribution of tropospheric NO2 using GOME narrow swath mode data

    NASA Astrophysics Data System (ADS)

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

    2004-09-01

    The Global Ozone Monitoring Experiment (GOME) allows the retrieval of tropospheric vertical column densities (VCDs) of NO2 on a global scale. Regions with enhanced industrial activity can clearly be detected, but the standard spatial resolution of the GOME ground pixels (320x40km2) is insufficient to resolve regional trace gas distributions or individual cities.

    Every 10 days within the nominal GOME operation, measurements are executed in the so called narrow swath mode with a much better spatial resolution (80x40km2). We use this data (1997-2001) to construct a detailed picture of the mean global tropospheric NO2 distribution. Since - due to the narrow swath - the global coverage of the high resolution observations is rather poor, it has proved to be essential to deseasonalize the single narrow swath mode observations to retrieve adequate mean maps. This is done by using the GOME backscan information.

    The retrieved high resolution map illustrates the shortcomings of the standard size GOME pixels and reveals an unprecedented wealth of details in the global distribution of tropospheric NO2. Localised spots of enhanced NO2 VCD can be directly associated to cities, heavy industry centers and even large power plants. Thus our result helps to check emission inventories.

    The small spatial extent of NO2 "hot spots" allows us to estimate an upper limit of the mean lifetime of boundary layer NOx of 17h on a global scale.

    The long time series of GOME data allows a quantitative comparison of the narrow swath mode data to the nominal resolution. Thus we can analyse the dependency of NO2 VCDs on pixel size. This is important for comparing GOME data to results of new satellite instruments like SCIAMACHY (launched March 2002 on ENVISAT), OMI (launched July 2004 on AURA) or GOME II (to be launched 2005) with an improved spatial resolution.

  7. Optical signatures of molecular dissymmetry: Combining theory with experiments to address stereochemical puzzles

    PubMed Central

    Mukhopadhyay, Parag; Wipf, Peter; Beratan, David N.

    2009-01-01

    Conspectus Modern chemistry emerged from the quest to describe the three-dimensional structure of molecules: van’t Hoff’s tetravalent carbon placed symmetry and dissymmetry at the heart of chemistry. In this Account, we explore how modern theory, synthesis, and spectroscopy can be used in concert to elucidate the symmetry and dissymmetry of molecules and their assemblies. Chiroptical spectroscopy—including optical rotatory dispersion (ORD), electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA)—measures the response of dissymmetric structures to electromagnetic radiation. This response can in turn reveal the arrangement of atoms in space, but deciphering the molecular information encoded in chiroptical spectra requires an effective theoretical approach. Although important correlations between ECD and molecular stereochemistry have existed for some time, a battery of accurate new theoretical methods that link a much wider range of chiroptical spectroscopies to structure have emerged over the last decade. The promise of this field is considerable: theory and spectroscopy can assist in assigning the relative and absolute configurations of complex products, in revealing the structure of non-covalent aggregates, in defining metrics for molecular diversity based upon polarization response, and in designing chirally imprinted nanomaterials. The physical organic chemistry of chirality is fascinating in its own right: defining atomic and group contributions to optical rotation (OR) is now possible. Although the common expectation is that chiroptical response is determined solely by a chiral solute’s electronic structure in a given environment, chiral imprinting effects on the surrounding medium and molecular assembly can, in fact, dominate the chiroptical signatures. The theoretical interpretation of chiroptical markers is challenging because the optical properties are subtle, which results from the strong

  8. 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

  9. 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.

  10. 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

  11. Optical signatures of molecular dissymmetry: combining theory with experiments to address stereochemical puzzles.

    PubMed

    Mukhopadhyay, Parag; Wipf, Peter; Beratan, David N

    2009-06-16

    Modern chemistry emerged from the quest to describe the three-dimensional structure of molecules: van't Hoff's tetravalent carbon placed symmetry and dissymmetry at the heart of chemistry. In this Account, we explore how modern theory, synthesis, and spectroscopy can be used in concert to elucidate the symmetry and dissymmetry of molecules and their assemblies. Chiroptical spectroscopy, including optical rotatory dispersion (ORD), electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA), measures the response of dissymmetric structures to electromagnetic radiation. This response can in turn reveal the arrangement of atoms in space, but deciphering the molecular information encoded in chiroptical spectra requires an effective theoretical approach. Although important correlations between ECD and molecular stereochemistry have existed for some time, a battery of accurate new theoretical methods that link a much wider range of chiroptical spectroscopies to structure have emerged over the past decade. The promise of this field is considerable: theory and spectroscopy can assist in assigning the relative and absolute configurations of complex products, revealing the structure of noncovalent aggregates, defining metrics for molecular diversity based on polarization response, and designing chirally imprinted nanomaterials. The physical organic chemistry of chirality is fascinating in its own right: defining atomic and group contributions to optical rotation (OR) is now possible. Although the common expectation is that chiroptical response is determined solely by a chiral solute's electronic structure in a given environment, chiral imprinting effects on the surrounding medium and molecular assembly can, in fact, dominate the chiroptical signatures. The theoretical interpretation of chiroptical markers is challenging because the optical properties are subtle, resulting from the strong electric dipole and the weaker electric

  12. 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

  13. 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

  14. 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

  15. Global free tropospheric NO2 abundances derived using a cloud slicing technique applied to satellite observations from the Aura Ozone Monitoring Instrument (OMI)

    NASA Astrophysics Data System (ADS)

    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 vs. 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 the

  16. Evaluation of a regional chemistry transport model using a newly developed regional OMI NO2 retrieval

    NASA Astrophysics Data System (ADS)

    Kuhlmann, G.; Lam, Y. F.; Cheung, H. M.; Hartl, A.; Fung, J. C. H.; Chan, P. W.; Wenig, M. O.

    2014-12-01

    In this paper, we evaluate a high-resolution chemistry transport model (CTM) (3 km x 3 km spatial resolution) with the new Hong Kong (HK) NO2 retrieval developed for the Ozone Monitoring Instrument (OMI) on-board the Aura satellite. The three-dimensional atmospheric chemistry was modelled in the Pearl River Delta (PRD) region in southern China by the Models-3 Community Multiscale Air Quality (CMAQ) modelling system from October 2006 to January 2007. In the HK NO2 retrieval, tropospheric air mass factors (AMF) were recalculated using high-resolution ancillary parameters of surface reflectance, NO2 profile shapes and aerosol profiles of which the latter two were taken from the CMAQ simulation. We also tested four different aerosol parametrizations. Ground level measurements by the PRD Regional Air Quality Monitoring (RAQM) network were used as additional independent measurements. The HK NO2 retrieval increases the NO2 vertical column densities (VCD) by (+31 ± 38) %, when compared to NASA's standard product (SP2), and reduces the mean bias (MB) between satellite and ground measurements by 26 percentage points from -41 to -15 %. The correlation coefficient r is low for both satellite datasets (r = 0.35) due to the high spatial variability of NO2 concentrations. The correlation between CMAQ and the RAQM network is low (r ≈ 0.3) and the model underestimates the NO2 concentrations in the north-western model domain (Foshan and Guangzhou). We compared the CMAQ NO2 time series of the two main plumes with our regional OMI NO2 product. The model overestimates the NO2 VCDs by about 15 % in Hong Kong and Shenzhen, while the correlation coefficient is satisfactory (r = 0.56). In Foshan and Guangzhou, the correlation is low (r = 0.37) and the model underestimates the VCDs strongly (MB = -40 %). In addition, we estimated that the OMI VCDs are also underestimated by about 10 to 20 % in Foshan and Guangzhou because of the influence of the model parameters on the AMF. In this study

  17. 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

  18. 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.

  19. Influence of satellite-derived photolysis rates and NOx emissions on Texas ozone modeling

    NASA Astrophysics Data System (ADS)

    Tang, W.; Cohan, D. S.; Pour-Biazar, A.; Lamsal, L. N.; White, A.; Xiao, X.; Zhou, W.; Henderson, B. H.; Lash, B.

    2014-09-01

    Uncertain photolysis rates and emission inventory impair the accuracy of state-level ozone (O3) regulatory modeling. Past studies have separately used satellite-observed clouds to correct the model-predicted photolysis rates, or satellite-constrained top-down NOx emissions to identify and reduce uncertainties in bottom-up NOx emissions. However, the joint application of multiple satellite-derived model inputs to improve O3 State Implementation Plan (SIP) modeling has rarely been explored. In this study, Geostationary Operational Environmental Satellite (GOES) observations of clouds are applied to derive the photolysis rates, replacing those used in Texas SIP modeling. This changes modeled O3 concentrations by up to 80 ppb and improves O3 simulations by reducing modeled normalized mean bias (NMB) and normalized mean error (NME) by up to 0.1. A sector-based discrete Kalman filter (DKF) inversion approach is incorporated with the Comprehensive Air Quality Model with extensions (CAMx)-Decoupled Direct Method (DDM) model to adjust Texas NOx emissions using a high resolution Ozone Monitoring Instrument (OMI) NO2 product. The discrepancy between OMI and CAMx NO2 vertical column densities (VCD) is further reduced by increasing modeled NOx lifetime and adding an artificial amount of NO2 in the upper troposphere. The sector-based DKF inversion tends to scale down area and non-road NOx emissions by 50%, leading to a 2-5 ppb decrease in ground 8 h O3 predictions. Model performance in simulating ground NO2 and O3 are improved using inverted NOx emissions, with 0.25 and 0.04 reductions in NMBs and 0.13 and 0.04 reductions in NMEs, respectively. Using both GOES-derived photolysis rates and OMI-constrained NOx emissions together reduces modeled NMB and NME by 0.05 and increases the model correlation with ground measurement in O3 simulations and makes O3 more sensitive to NOx emissions in the O3 non-attainment areas.

  20. 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