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  1. Phil Ochs: No Place in This World

    ERIC Educational Resources Information Center

    Doughty, Howard A.

    2005-01-01

    Phil Ochs was a prominent topical songwriter and singer in the 1960s. He was conventionally considered second only to Bob Dylan in terms of popularity, creativity and influence in the specific genre of contemporary folk music commonly known as "protest music." Whereas Dylan successfully reinvented himself many times in terms of his musical style…

  2. Atmospheric chemistry of CF3CF2OCH3

    NASA Astrophysics Data System (ADS)

    Østerstrøm, Freja F.; Nielsen, Ole John; Wallington, Timothy J.

    2016-06-01

    Smog chamber Fourier transform infrared techniques were used to investigate the kinetics of the reaction of CF3CF2OCH3 with Cl atoms and OH radicals: k(Cl + CF3CF2OCH3) = (1.09 ± 0.16) × 10-13 and k(OH + CF3CF2OCH3) = (1.28 ± 0.19) × 10-14 cm3 molecule-1 s-1 in 700 Torr total pressure of N2/O2 at 296 ± 2 K. The Cl-initiated oxidation of CF3CF2OCH3 gives CF3CF2OCHO in a yield indistinguishable from 100%. An estimate of k(Cl + CF3CF2OCHO) = (1.18 ± 0.34) × 10-14 cm3 molecule-1 s-1 is provided. Based on the OH reaction rate, the atmospheric lifetime of CF3CF2OCH3 is estimated to be 5.0 years. The 100-year time horizon global warming potential of CF3CF2OCH3 is estimated to be 585. The atmospheric impact of CF3CF2OCH3 is discussed.

  3. Computational exploration of regioselectivity and atmospheric lifetime in NO3-initiated reactions of CH3OCH3 and CH3OCH2CH3.

    PubMed

    Ye, Jin-Ting; Bai, Feng-Yang; Shi, Shao-Qing; Pan, Xiu-Mei

    2017-03-01

    The NO3-initiated reactions of CH3OCH3 and CH3OCH2CH3 have been investigated by the BHandHLYP method in conjunction with the 6-311G(d,p) basis set. Thermodynamic and kinetic data are further refined using the comparatively accurate CCSD(T) method. According to the values of reaction enthalpies (ΔHr,298(θ)) and reaction Gibbs free energies (ΔGr,298(θ)) from CH3OCH2CH3 with NO3 system, we find that H-abstraction pathway from the α-CH2 group is more exothermic. It is further confirmed by the calculated CH bond dissociation energy of CH3OCH2CH3 molecule. All the rate constants, computed through means of canonical variational transition state with small-curvature tunneling correction, are fitted to the three-parameter expressions k1=1.54×10(-23)T(3.34)exp(-1035.53/T) and k2=3.55×10(-26)T(4.31)exp(-281.24/T)cm(3)molecule(-1)s(-1) and branching ratios are computed over the temperature range 200-600K. The branching ratios are also discussed. The atmospheric lifetimes of CH3OCH3 and CH3OCH2CH3 determined by the NO3 radical are about 270 and 29days, respectively. Copyright © 2017. Published by Elsevier Inc.

  4. Water-soluble derivatives of 25-OCH3-PPD and their anti-proliferative activities.

    PubMed

    Zhou, Wu-Xi; Sun, Yuan-Yuan; Yuan, Wei-Hui; Zhao, Yu-Qing

    2017-03-18

    (20R)-25-Methoxyl-dammarane-3β,12β,20-triol (25-OCH3-PPD, AD-1) is a dammarane-type sapogenin showing anti-tumor potential. In the search for new anti-tumor agents with higher potency than our previously identified compound 25-OCH3-PPD, 11 novel sulfamic acid and diacid derivatives that could improve water solubility and contribute to good drug potency and pharmacokinetic profiles were designed and synthesized. Their in vitro anti-tumor activities in MCF-7, A-549, HCT-116, and BGC-823 cell lines and one normal cell line were tested by standard MTT assay. Results showed that compared with compound 25-OCH3-PPD, compounds 1, 4, and 5 exhibited higher cytotoxic activity on almost all cell lines, together with lower toxicity in the normal cell. In particular, compound 1 exhibited the best anti-tumor activity in the in vitro assays. The water solubility of 25-OCH3-PPD and its derivatives was tested and the results showed that the solubility of 25-OCH3-PPD sulfamic acid and diacid derivatives were better than that of 25-OCH3-PPD in water, which may provide valuable data for the research and development of new anti-tumor agents.

  5. Shock tube investigation of CH3 + CH3OCH3.

    PubMed

    Tranter, Robert S; Lynch, Patrick T; Annesley, Christopher J

    2012-07-12

    The title reaction has been investigated in a diaphragmless shock tube by laser schlieren densitometry over the temperature range 1163-1629 K and pressures of 60, 120, and 240 Torr. Methyl radicals were produced by dissociation of 2,3-butanedione in the presence of an excess of dimethyl ether. Rate coefficients for CH(3) + CH(3)OCH(3) were obtained from simulations of the experimental data yielding the following expression which is valid over the range 1100-1700 K: k = (10.19 ± 3.0)T(3.78) exp((-4878/T)) cm(3) mol(-1)s(-1). The experimental results are in good agreement with estimates by Curran and co-workers [Fischer, S. L.; Dryer, F. L.; Curran, H. J. Int. J. Chem. Kinet.2000, 32 (12), 713-740. Curran, H. J.; Fischer, S. L.; Dryer, F. L. Int. J. Chem. Kinet.2000, 32 (12), 741-759] but about a factor of 2.6 lower than those of Zhao et al. [Zhao, Z.; Chaos, M.; Kazakov, A.; Dryer, F. L. Int. J. Chem. Kinet.2008, 40 (1), 1-18].

  6. Analysis of the Vibrational Spectra of P_3N_3(OCH_2CF_3)_6 and P_4N_4(OCH_2CF_3)_8

    NASA Astrophysics Data System (ADS)

    King, Adrian K.; Plant, David F.; Golding, Peter; Lawson, Michael A.; Davies, Paul B.

    2011-06-01

    The cyclic phosphazene trimer P_3N_3(OCH_2CF_3)_6 and the related cyclic tetramer P_4N_4(OCH_2CF_3)_8 have been proposed as the major low-to-medium temperature pyrolysis products of the parent polyphosphazene (PN(OCH_2CF_3)_2)_n. Recently, both molecules have been synthesized, isolated and their vapour-phase vibrational spectra recorded using a high-resolution FTIR instrument. The interpretation of these spectra is achieved primarily by comparison with the results of high-quality density functional calculations, which enable the principal absorption features to be assigned and conclusions to be drawn regarding the geometries and conformations adopted by both molecules. These in turn allow interesting comparisons to be made with analogous cyclic halo-phosphazenes such as P_3N_3Cl_6 and P_4N_4Cl_8. Work to record in situ the spectra of the vapour-phase pyrolysis products of (PN(OCH_2CF_3)_2)_n and to analyse these results in terms of the tetramer and trimer spectra will also be presented. S. V. Peddada and J. H. Magill Macromolecules 16 (1983) 1258-1264. H. R. Allcock, G. S. McDonnell, G. H. Riding, and I. Manners Chem. Mater. 2 (1990) 425-432. T. R. Manley and D. A. Williams Spectrochimica Acta 23A (1966) 149-165. V. Varma, J. R. Fernandez and C. N. R. Rao J. Mol. Struct. 198 (1989) 403-412.

  7. Direct amidation of unprotected amino acids using B(OCH2CF3)3.

    PubMed

    Lanigan, Rachel M; Karaluka, Valerija; Sabatini, Marco T; Starkov, Pavel; Badland, Matthew; Boulton, Lee; Sheppard, Tom D

    2016-07-07

    A commercially available borate ester, B(OCH2CF3)3, can be used to achieve protecting-group free direct amidation of α-amino acids with a range of amines in cyclopentyl methyl ether. The method can be applied to the synthesis of medicinally relevant compounds, and can be scaled up to obtain gram quantities of products.

  8. Atmospheric degradation mechanism of CF{sub 3}OCH{sub 3}

    SciTech Connect

    Christensen, L.K.; Wallington, T.J.; Guschin, A.; Hurley, M.D.

    1999-05-27

    Recognition of the adverse effect of chlorofluorocarbon (CFC) release into the atmosphere has led to an international effort to replace CFCs with environmentally acceptable alternatives. Hydrofluoroethers (HFEs) are a class of compounds which have been developed to replace CFCs in applications such as the cleaning of electronic equipment, heat transfer agents in refrigeration systems, and carrier fluids for lubricant deposition. HFEs are volatile compounds and are released into the atmosphere when used. CF{sub 3}OCH{sub 3} has not been used commercially but is one of the simplest fluoroethers and serves as a model compound for the group of fluorinated ethers. A smog chamber/FTIR technique was used to study the Cl atom initiated oxidation of CF{sub 3}OCH{sub 3} in 700 Torr of N{sub 2}/O{sub 2} at 296 K. Using relative rate techniques it was determined that {kappa}(Cl + CF{sub 3}OCH{sub 3}) = (1.4 {+-} 0.2) {times} 10{sup {minus}13} and {kappa}(Cl + CF{sub 3}OC(O)H) = (9.8 {+-} 1.2) {times} 10{sup {minus}15} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. At 700 Torr of N{sub 2}/O{sub 2} diluent at 296 K reaction with O{sub 2} is the only loss mechanism of the CF{sub 3}OCH{sub 2}O{sup {sm_bullet}} radical. The infrared spectra of the peroxy nitrates CF{sub 3}OCH{sub 2}O{sub 2}NO{sub 2} and CF{sub 3}OC(O)O{sub 2}NO{sub 2} were recorded and compared to the nonfluorinated analogues CH{sub 3}OCH{sub 2}O{sub 2}NO{sub 2} and CH{sub 3}OC(O)O{sub 2}NO{sub 2}. The thermal decomposition rate of CF{sub 3}OC(O)NO{sub 2} is (2.3 {+-} 0.1) {times} 10{sup {minus}4} s{sup {minus}1} in 700 Torr of N{sub 2} at 295.8 K. The reaction of CF{sub 3}OC(O)O{sub 2} radicals with HO{sub 2} radicals gives CF{sub 3}OC(O)H in a yield of (80 {+-} 11)%. The results are discussed with respect to the atmospheric degradation mechanism of CF{sub 3}OCH{sub 3} and other ethers.

  9. Study and orientation of the Mt. Oche `Dragon House' in Euboea, Greece

    NASA Astrophysics Data System (ADS)

    Theodossiou, E.; Manimanis, V. N.; Katsiotis, M.; Papanikolaou, D.

    2009-07-01

    In southern Euboea, Central Greece, there are several megalithic buildings known as ‘drakospita’ (or dragon houses) whose builders and purpose are unknown. On 22 March 2002 and 4 July 2004 we visited the bestpreserved of all drakospita on top of Mt. Oche, measured its dimensions and calculated its orientation based on the azimuth of sunset and moonrise. A Sirius-rise orientation corresponding to ca 1100 B.C., not inconsistent with previous archaeological dating based on artefacts found inside the structure, indicates a religious/astronomical purpose for the building. It could probably be argued that at least the famous drakospito at Mt. Oche was not only a place of worship but also an ancient astronomical observatory.

  10. The ether lipid ET-18-OCH3 increases cytosolic Ca2+ concentrations in Madin Darby canine kidney cells.

    PubMed

    Jan, C R; Wu, S N; Tseng, C J

    1999-07-01

    The effect of the ether lipid 1-O-octadecyl-2-O-methyl-sn-glycero-3-phosphorylcholine (ET-18-OCH3) on the intracellular free Ca2+ concentration ([Ca2+]i) in Madin Darby canine kidney (MDCK) cells was studied using fura-2 as the Ca2+ probe. In Ca2+ medium, ET-18-OCH3 induced a significant rise in [Ca2+]i at concentrations between 10-100 microM with a concentration-dependent delay of 45-175 s. The [Ca2+]i signal was composed of a gradual rise and a sustained plateau. In Ca2+-free medium, ET-18-OCH3 (10-100 microM) induced a Ca2+ release from internal Ca2+ stores with a concentration-dependent delay of 45-175 s. This discharge of internal Ca2+ triggered capacitative Ca2+ entry in a concentration-dependent manner. This capacitative Ca2+ entry was not inhibited by econazole (25 microM), 1-[beta-[3-(4-methoxyphenyl)propoxy]-4-methoxyphenethyl]-1H-imidazole hydrochloride (SKF96365; 50 microM), nifedipine (10 microM), verapamil (10 microM), diltiazem (10 microM) and cadmium (0.5 microM). Methyl 2-(phenylthio)ethyl-1,4-dihydro-2,4,6-trimethylpyridine-3,5-dicarboxylat e (PCA-4248), a platelet-activating factor (PAF) receptor antagonist, inhibited 25 microM ET-18-OCH3-induced [Ca2+]i rise in a concentration-dependent manner between 1-20 microM, with 20 microM exerting a complete block. The [Ca2+]i rise induced by ET-18-OCH3 (25 microM) was not altered when the production of inositol 1,4,5-trisphosphate (IP3) was suppressed by the phospholipase C inhibitor U73122 (2 microM), but was partly inhibited by the phospholipase D inhibitor propranolol (0.1 mM) or the phospholipase A2 inhibitor aristolochic acid (20-40 microM). In Ca2+-free medium, pretreatment with 25 microM ET-18-OCH3 completely depleted the endoplasmic reticulum Ca2+ pump inhibitor thapsigargin-sensitive Ca2+ store. In contrast, pretreatment with thapsigargin abolished 0.1 mM ATP-induced [Ca2+]i rise without altering the ET-18-OCH3-induced [Ca2+]i rise. This suggests that ET-18-OCH3 depleted thapsigargin

  11. Phage resistance of a marine bacterium, Roseobacter denitrificans OCh114, as revealed by comparative proteomics.

    PubMed

    Huang, Chunxiao; Zhang, Yongyu; Jiao, Nianzhi

    2010-08-01

    Roseobacter is a dominant lineage in the marine environment. This group of bacteria is diverse in terms of both their phylogenetic composition and their physiological potential. Roseobacter denitrificans OCh114 is one of the most studied bacteria of the Roseobacter lineage. Recently, a lytic phage (RDJLPhi1) that infects this bacterium was isolated and a mutant strain (M1) of OCh114 that is resistant to RDJLPhi1 was also obtained. Here, we investigate the mechanisms supporting phage resistance of M1. Our results excluded the possibilities of several phage resistance mechanisms, including abortive infection, lysogeny, and the clustered regularly interspaced short palindromic repeats (CRISPRs) related mechanism. Adsorption kinetics assays revealed that adsorption inhibition might be a potential cause for the phage resistance of M1. Comparative proteomic analysis of M1 and OCh114 revealed significant changes in the membrane protein compliment of these bacteria. Five membrane proteins with important biological functions were significantly down-regulated in the phage-resistant M1. Meanwhile, several outer membrane porins with different modifications and an OmpA family domain protein were markedly up-regulated. We hypothesize that the down-regulated membrane proteins in M1 may serve as the potential phage receptors, whose absence prevented the adsorption of phage RDJLPhi1 to host cells and subsequent infection.

  12. Natural product ginsenoside 25-OCH3-PPD inhibits breast cancer growth and metastasis through down-regulating MDM2.

    PubMed

    Wang, Wei; Zhang, Xu; Qin, Jiang-Jiang; Voruganti, Sukesh; Nag, Subhasree Ashok; Wang, Ming-Hai; Wang, Hui; Zhang, Ruiwen

    2012-01-01

    Although ginseng and related herbs have a long history of utility for various health benefits, their application in cancer therapy and underlying mechanisms of action are not fully understood. Our recent work has shown that 20(S)-25-methoxyl-dammarane-3β, 12β, 20-triol (25-OCH(3)-PPD), a newly identified ginsenoside from Panax notoginseng, exerts activities against a variety of cancer cells in vitro and in vivo. This study was designed to investigate its anti-breast cancer activity and the underlying mechanisms of action. We observed that 25-OCH(3)-PPD decreased the survival of breast cancer cells by induction of apoptosis and G1 phase arrest and inhibited the growth of breast cancer xenografts in vivo. We further demonstrated that, in a dose- and time-dependent manner, 25-OCH(3)-PPD inhibited MDM2 expression at both transcriptional and post-translational levels in human breast cancer cells with various p53 statuses (wild type and mutant). Moreover, 25-OCH(3)-PPD inhibited in vitro cell migration, reduced the expression of epithelial-to-mesenchymal transition (EMT) markers, and prevented in vivo metastasis of breast cancer. In summary, 25-OCH(3)-PPD is a potential therapeutic and anti-metastatic agent for human breast cancer through down-regulating MDM2. Further preclinical and clinical development of this agent is warranted.

  13. Diversity of Ochrobactrum species in food animals, antibiotic resistance phenotypes and polymorphisms in the blaOCH gene.

    PubMed

    Alonso, Carla Andrea; Kwabugge, Yakubu A; Anyanwu, Madubuike U; Torres, Carmen; Chah, Kennedy F

    2017-09-15

    Twenty-six lactose non-fermenting, oxidase, urease and citrate-positive Gram-negative rods, isolated from broiler chickens, pigs and cattle at slaughter, were subjected to the matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry and 16S rDNA sequencing for identification. Susceptibility to 14 antimicrobials was determined by the disc diffusion method. Ochrobactrum isolates resistant to third-generation cephalosporins were PCR-screened for the presence of the Ochrobactrum anthropi ampC gene (blaOCH). A 547-bp internal segment of blaOCH in the Ochrobactrum spp isolates was amplified with a newly designed primer set, and a phylogenetic reconstruction based on the complete amino acid sequence of blaOCH obtained from nine Ochrobactrum strains in our collection and 20 O. anthropi available in the GenBank was undertaken. All the Ochrobactrum isolates were resistant to the expanded-spectrum beta-lactams and streptomycin. None of the isolates was resistant to imipenem while 41.7% to 50.0% of them were resistant to fluoroquinolones. The blaOCH gene was detected in 16 (66.7%) and 20 (83.3%) of the 24 Ochrobactrum isolates (O. intermedium/O. tritici species), using primers designed for O. anthropi and the newly designed primer set, respectively. Six blaOCH variants grouped into two divergent clusters were identified. This is the first report of the complete nucleotide sequence of the blaOCH gene in non-antropi Ochrobactrum species. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  14. A General Method for Imine Formation Using B(OCH2CF3)3.

    PubMed

    Reeves, Jonathan T; Visco, Michael D; Marsini, Maurice A; Grinberg, Nelu; Busacca, Carl A; Mattson, Anita E; Senanayake, Chris H

    2015-05-15

    Tris(2,2,2-trifluoroethyl)borate [B(OCH2CF3)3] was found to be a mild and general reagent for the formation of a variety of imines by condensation of amides or amines with carbonyl compounds. N-Sulfinyl, N-toluenesulfonyl, N-(dimethylamino)sulfamoyl, N-diphenylphosphinoyl, N-(α-methylbenzyl), and N-(4-methoxyphenyl) aldimines are all accessible using this reagent at room temperature. The reactions are operationally simple, and the products are obtained without special workup or isolation procedures.

  15. Comparison Of Several Metrology Techniques For In-line Process Monitoring Of Porous SiOCH

    SciTech Connect

    Fossati, D.; Imbert, G.; Beitia, C.; Yu, L.; Plantier, L.; Volpi, F.

    2007-09-26

    As porous SiOCH is a widely used inter-metal dielectric for 65 nm nodes and below, the control of its elaboration process by in-line monitoring is necessary to guarantee successful integration of the material. In this paper, the sensitivities of several non-destructive metrology techniques towards the film elaboration process drifts are investigated. It appears that the two steps of the process should be monitored separately and that corona charge method is the most sensitive technique of the review for this application.

  16. Functional characterization of the gene FoOCH1 encoding a putative α-1,6-mannosyltransferase in Fusarium oxysporum f. sp. cubense.

    PubMed

    Li, Min-Hui; Xie, Xiao-Ling; Lin, Xian-Feng; Shi, Jin-Xiu; Ding, Zhao-Jian; Ling, Jin-Feng; Xi, Ping-Gen; Zhou, Jia-Nuan; Leng, Yueqiang; Zhong, Shaobin; Jiang, Zi-De

    2014-04-01

    Fusarium oxysporum f. sp. cubense (FOC) is the causal agent of banana Fusarium wilt and has become one of the most destructive pathogens threatening the banana production worldwide. However, few genes related to morphogenesis and pathogenicity of this fungal pathogen have been functionally characterized. In this study, we identified and characterized the disrupted gene in a T-DNA insertional mutant (L953) of FOC with significantly reduced virulence on banana plants. The gene disrupted by T-DNA insertion in L953 harbors an open reading frame, which encodes a protein with homology to α-1,6-mannosyltransferase (OCH1) in fungi. The deletion mutants (ΔFoOCH1) of the OCH1 orthologue (FoOCH1) in FOC were impaired in fungal growth, exhibited brighter staining with fluorescein isothiocyanate (FITC)-Concanavalin A, had less cell wall proteins and secreted more proteins into liquid media than the wild type. Furthermore, the mutation or deletion of FoOCH1 led to loss of ability to penetrate cellophane membrane and decline in hyphal attachment and colonization as well as virulence to the banana host. The mutant phenotypes were fully restored by complementation with the wild type FoOCH1 gene. Our data provide a first evidence for the critical role of FoOCH1 in maintenance of cell wall integrity and virulence of F. oxysporum f. sp. cubense. Copyright © 2014 Elsevier Inc. All rights reserved.

  17. Mechanism of plasma-induced damage to low-k SiOCH films during plasma ashing of organic resists

    SciTech Connect

    Takeda, Keigo; Miyawaki, Yudai; Takashima, Seigo; Fukasawa, Masanaga; Oshima, Keiji; Nagahata, Kazunori; Tatsumi, Tetsuya; Hori, Masaru

    2011-02-01

    Plasma-induced damage to porous SiOCH (p-SiOCH) films during organic resist film ashing using dual-frequency capacitively coupled O{sub 2} plasmas was investigated using the pallet for plasma evaluation method developed by our group. The damage was characterized by ellipsometry and Fourier-transform infrared spectroscopy. Individual and synergetic damage associated with vacuum ultraviolet (VUV) and UV radiation, radicals, and ions in the O{sub 2} plasma were clarified. It was found that the damage was caused not only by radicals but also by synergetic reactions of radicals with VUV and UV radiation emitted by the plasmas. It is noteworthy that the damage induced by plasma exposure without ion bombardment was larger than the damage with ion bombardment. These results differed from those obtained using an H{sub 2}/N{sub 2} plasma for resist ashing. Finally, the mechanism of damage to p-SiOCH caused by O{sub 2} and H{sub 2}/N{sub 2} plasma ashing of organic resist films is discussed. These results are very important in understanding the mechanism of plasma-induced damage to p-SiOCH films.

  18. Disproportionation and thermochemical sulfate reduction reactions in S-H2O-CH4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

    NASA Astrophysics Data System (ADS)

    Yuan, Shunda; Chou, I.-Ming; Burruss, Robert C.

    2013-10-01

    Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCCs). After a heating period ranging from 24 to 2160 h (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (<200 °C) than those of any previous experiments; (3) the disproportionation and TSR reactions in the S-H2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures >200 °C that can be reached by deep drilling for hydrocarbon resources.

  19. The mechanism of low-k SiOCH film modification by oxygen atoms

    SciTech Connect

    Braginsky, O. V.; Kovalev, A. S.; Lopaev, D. V.; Malykhin, E. M.; Mankelevich, Yu. A.; Rakhimova, T. V.; Rakhimov, A. T.; Vasilieva, A. N.; Zyryanov, S. M.; Baklanov, M. R.

    2010-10-15

    The interaction of oxygen atoms with three types of plasma enhanced chemical vapor deposition low-k SiOCH films is studied. The samples were treated by O atoms in the far plasma afterglow conditions in a special experimental system designed for this study. The experimental system allowed avoiding the effect of ions and vacuum ultraviolet (VUV) photons on surface reactions and controlling the oxygen atom concentration over the samples. Fourier-transform infrared spectroscopy, x-ray fluorescence, and atomic force microscopy techniques were used to analyze the changes occurring in low-k films. Monte Carlo model for O atom interaction with low-k material that includes penetration, recombination, and reactions with methyl groups was developed. It is shown that the surface recombination on the pore wall surface determines the profile and penetration depth of O atoms into the films. The reaction of O atoms with methyl groups has lower probability and therefore proceeds in the background mode.

  20. Theoretical study and rate constant calculation of the CH2O+CH3 reaction

    NASA Astrophysics Data System (ADS)

    Liu, Jing-yao; Li, Ze-sheng; Wu, Jia-yan; Wei, Zhi-gang; Zhang, Gang; Sun, Chia-chung

    2003-10-01

    The potential energy surface of the CH2O+CH3 reaction is explored at the MP2/6-311++G(d,p), MP4SDQ/6-311G(d,p), and QCISD(T)/6-311+G(3df,2p) (single point) levels of theory. Theoretical calculations suggest that the major product channel (R1) is the hydrogen abstraction leading to the product P1 CHO+CH4 (R1), while the addition process leading to P2H+CH3CHO (R2) appears to be negligibly small. The calculated enthalpies and dissociation activation energies for CH3CH2O and CH3OCH2 radicals involved in the reaction are in line with the experimental values. Dual-level dynamics calculation is carried out for the direct hydrogen abstraction channel. The energy profile of (R1) is refined with the interpolated single-point energies (ISPE) method at the QCISD(T)//MP2 level. The rate constants, which are evaluated by canonical variational transition-state theory (CVT) including small-curvature tunneling (SCT) correction, are in good agreement with the available experimental data. It is shown that tunneling effect plays a significant role in the rate constant calculation; and as a result, the CVT/SCT rate constants exhibit typical non-Arrhenius behavior over a wide temperature range 300-2000 K. The three parameter expression is k=6.35×10-26 T4.4 exp(-2450/T) cm3 molecule-1 s-1.

  1. Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).

    PubMed

    Ard, Shaun G; Johnson, Ryan S; Martinez, Oscar; Shuman, Nicholas S; Guo, Hua; Troe, Jürgen; Viggiano, Albert

    2016-07-14

    The kinetics of the reaction CH3OCH3 + Fe(+) has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe(+)O(CH3)2 adducts and of Fe(+)OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results.

  2. Direct synthesis of amides from carboxylic acids and amines using B(OCH2CF3)3.

    PubMed

    Lanigan, Rachel M; Starkov, Pavel; Sheppard, Tom D

    2013-05-03

    B(OCH2CF3)3, prepared from readily available B2O3 and 2,2,2-trifluoroethanol, is as an effective reagent for the direct amidation of a variety of carboxylic acids with a broad range of amines. In most cases, the amide products can be purified by a simple filtration procedure using commercially available resins, with no need for aqueous workup or chromatography. The amidation of N-protected amino acids with both primary and secondary amines proceeds effectively, with very low levels of racemization. B(OCH2CF3)3 can also be used for the formylation of a range of amines in good to excellent yield, via transamidation of dimethylformamide.

  3. Direct Synthesis of Amides from Carboxylic Acids and Amines Using B(OCH2CF3)3

    PubMed Central

    2013-01-01

    B(OCH2CF3)3, prepared from readily available B2O3 and 2,2,2-trifluoroethanol, is as an effective reagent for the direct amidation of a variety of carboxylic acids with a broad range of amines. In most cases, the amide products can be purified by a simple filtration procedure using commercially available resins, with no need for aqueous workup or chromatography. The amidation of N-protected amino acids with both primary and secondary amines proceeds effectively, with very low levels of racemization. B(OCH2CF3)3 can also be used for the formylation of a range of amines in good to excellent yield, via transamidation of dimethylformamide. PMID:23586467

  4. Atmospheric chemistry of CF{sub 3}C(O)OCH{sub 2}CF{sub 3}: UV spectra and kinetic data for CF{sub 3}C(O)OCH({sm_bullet})CF{sub 3} and CF{sub 3}C(O)OCH(OO{sm_bullet})CF{sub 3} radicals, and atmospheric fate of CF{sub 3}C(O)OCH(O{sm_bullet})CF{sub 3} radicals

    SciTech Connect

    Stein, T.N.N.; Christensen, L.K.; Platz, J.; Sehested, J.; Nielsen, O.J.; Wallington, T.J.

    1999-07-22

    Recognition of the adverse effect of chlorofluorocarbon (CFC) release into the atmosphere has led to an international effort to replace CFCs with environmentally acceptable alternatives. Hydrofluoroethers (HFEs) are fluids designed to replace CFCs in applications such as the cleaning of electronic equipment, heat transfer agents in refrigeration systems, and carrier fluids for lubricant deposition. HFEs are volatile compounds and will be released into the atmosphere during its use. In the atmosphere, photochemical oxidation of HFEs will lead to the formation of fluorinated esters and fluorinated formates. The atmospheric fate of these products is unknown at the present. To improve their understanding of the atmospheric chemistry of esters the authors have studied the atmospheric chemistry of 2,2,2-trifluoroethyltrifluoroacetate CF{sub 3}C(O)OCH{sub 2}CF{sub 3} (bp = 55.0 C). This compound provides insight into the behavior of alkyl, alkyl peroxy, and alkoxy radicals formed {alpha} to the ester functionality. The atmospheric fate of CF{sub 3}C(O)OCH(O{sup {sm_bullet}})CF{sub 3} radicals was investigated in a FTIR smog chamber. Three loss processes for the CF{sub 3}C(O)OCH(O{sup {sm_bullet}})CF{sub 3} radicals were identified at 296 K and 700 Torr total pressure, reaction with O{sub 2} to form CF{sub 3}C(O)OC(O)CF{sub 3}, {alpha}-rearrangement to form CF{sub 3}C(O){sm_bullet} radicals and CF{sub 3}C(O)OH, and decomposition via a mechanism which is unclear. In 760 Torr of air at 296 K, 65% of the CF{sub 3}C(O)OCH(O{sm_bullet})CF{sub 3} radicals react with oxygen, 18% undergo {alpha}-rearrangement, while the fate of the remaining 17% is unclear.

  5. Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

    PubMed

    Sarkar, Sounak; Li, Shan; Wayland, Bradford B

    2011-04-18

    Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

  6. Astronomical Orientations Of Dragon Houses (Laka Palli, Kapsala, Oche) And Armena Gate (Euboea, Greece)

    NASA Astrophysics Data System (ADS)

    Liritzis, I.; Artelaris, G.

    The preliminary investigation of the astronomical orientation of monuments at Styra, southern Euboea, includes the triple so called 'dragon house' complex at Laka Palli, one dragon house at Kapsala and one on the summit of Mount Oche, and a monumental gate in the megalithic fortification wall at Armena. Recent luminescence testing dates these remains to approximately the Classical period with apparent re-use in Roman and later times. Thus far no definite astronomical orientation has been determined in the layout of the structures and no celestial stone markers or similar features have been found associated with the dragon houses, however, the relationship of significant stars, constellations and solar stands was well known in antiquity, and the limited results presented here suggests the possibility for further investigation. This study, which considered possible orientations related to sun rise and sun set for the summer and winter solstice, as well as, alignments towards equinoxes and major bright stars and constellations, did observe a general preference for a southern orientation at most of the sites and a possible feature for time observations in the dragon house complex at Laka Palli.

  7. High pressure Raman spectroscopy of H2O-CH3OH mixtures.

    PubMed

    Hsieh, Wen-Pin; Chien, Yu-Hsiang

    2015-02-23

    Complex intra-molecular interactions and the hydrogen-bonding network in H2O-volatile mixtures play critical roles in many dynamics processes in physical chemistry, biology, and Earth and planetary sciences. We used high pressure Raman spectroscopy to study the pressure evolution of vibrational frequencies and bonding behavior in H2O-CH3OH mixtures. We found that the presence of low CH3OH content in H2O increases the transition pressure where water crystallizes to ice VI, but does not significantly change the pressure where ice VI transforms to ice VII. Furthermore, the stiffening rates of C-H stretching frequencies dω/dP in CH3OH significantly decrease upon the crystallization of water, and the softening rates of the O-H stretching frequencies of ice VII are suppressed over a narrow pressure range, after which the frequencies of these modes shift with pressure in ways similar to pure CH3OH and ice VII, respectively. Such complex pressure evolution of Raman frequencies along with pronounced variations in Raman intensities of CH3OH within the sample, and the hysteresis of the water-ice VI phase transition suggest pressure-induced segregation of low content CH3OH from ice VII. These findings indicate the significant influence of volatiles on the crystallization of sub-surface ocean and thermal evolution within large icy planets and satellites.

  8. Towards understanding intrinsic degradation and breakdown mechanisms in SiOCH low-k dielectrics

    SciTech Connect

    Wu, C. De Wolf, I.; Li, Y.; Ciofi, I.; Kauerauf, Th.; Bömmels, J.; Tőkei, Zs.; Croes, K.

    2015-02-14

    The degradation and breakdown mechanisms of a SiOCH low-k material with k = 2.3 (25% porosity) and thicknesses ranging from 90 nm to 20 nm were investigated. By combining the time dependent dielectric breakdown data at positive/negative bias stress with the thickness scaling results, dielectric failure is proven to be intrinsic and not influenced by copper drift or metal barrier deposition induced dielectric damage. It is shown that stress induced leakage current (SILC) can be used as a measure of dielectric degradation. Therefore, low field lifetimes can be safely estimated using SILC extrapolation. Based on our results, both the impact damage model and the power law model have a good accuracy for low field lifetime prediction. Recovery and anneal experiments are used to study the physical nature causing the observed negative flatband voltage shifts in our metal-insulator-semiconductor planar capacitor structures, where hydrogen induced unstable fast and slow donor type interface states are hypothesized to be the root cause of the observed shifts. We suggest that atomic hydrogen is released from the dielectric during electron injection and migrates to the interfacial region. Our model is further supported by an observed irreversible SILC change during the recovery and anneal studies. The degradation mechanism proposed in this work, supported by the low field lifetime data, provides a feasible explanation for intrinsic low-k dielectric failure.

  9. Disproportionation and Thermochemical Sulfate Reduction Reactions in S-H2O-CH4 and S-D2O-CH4 Systems from 200 to 340 °C at Elevated Pressures

    NASA Astrophysics Data System (ADS)

    Chou, I.; Yuan, S.; Burruss, R. C.

    2010-12-01

    Elemental sulfur plays significant roles in thermochemical sulfate reduction (TSR) reactions as a transient intermediate oxidation state compound, by-product, or catalyst. However, the mechanisms of the reactions in S-H2O-hydrocarbon systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules. After a heating period ranging from one to 90 days, the quenched samples were analyzed by Raman spectroscopy. Our results showed that the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and HSO4-. We also observed that the amounts of SO42- and HSO4- decreased for the samples quenched from 250 and 340 °C, and at the same time the amounts of CO2 and H2S increased. To demonstrate that the observed consumption of SO42- and HSO4- in the S-H2O-CH4 system at 300 °C was due to TSR instead of the back reaction between SO42- (or HSO4-) and H2S to form S during and after quench, we introduced 1m ZnBr2 to remove H2S as a ZnS precipitate, as soon as it formed. In these experiments sulfate species decreased and CO2 and H2S increased consistent with TSR and no back reaction. When compared with previously published experiments, our temperatures between 250 and 340 °C are much closer to natural systems (<200 °C) with documented TSR. Also, to demonstrate the relationship between disproportionation and TSR reactions in the S-H2O-CH4 system, we conducted experiments in the S-D2O-CH4 system at 250 and 300 °C. Only small Raman signals for CO2 and no signals for H2S and D2S were detected in the sample quenched from 250 °C, indicating that both the disproportionation reaction and the TSR reaction were very slow at this temperature. After heating at 300 °C for 40 h, Raman signals of the quenched sample indicated significant amount of D2S was produced through the

  10. H2/N2 plasma damage on porous dielectric SiOCH film evaluated by in situ film characterization and plasma diagnostics

    NASA Astrophysics Data System (ADS)

    Yamamoto, Hiroshi; Takeda, Keigo; Ishikawa, Kenji; Ito, Masafumi; Sekine, Makoto; Hori, Masaru; Kaminatsui, Takeshi; Hayashi, Hisataka; Sakai, Itsuko; Ohiwa, Tokuhisa

    2011-04-01

    This study investigates the mechanism of H2/N2 plasma ashing damage of porous SiOCH films. Porous SiOCH films were treated by a H2/N2 plasma using a 100-MHz capacitively coupled plasma etcher. The impact of ions, radicals, and vacuum ultraviolet radiation on the porous SiOCH films was investigated using in situ bulk analysis techniques such as spectroscopic ellipsometry and Fourier-transform infrared spectroscopy and ex situ film characterization techniques such as dynamic secondary ion mass spectrometry and x-ray photoelectron spectroscopy. In addition, plasma analysis including vacuum ultraviolet absorption spectroscopy was performed. The film characterization and plasma analysis show that the extraction of methyl by H radicals was enhanced by light while N radicals were responsible for inhibit the extraction of Si-CH3 bonds by forming nitride layer. The H2/N2 plasma damage mechanism is discussed based on characterization of the film and plasma diagnostics.

  11. Investigation of the O+allyl addition/elimination reaction pathways from the OCH(2)CHCH(2) radical intermediate.

    PubMed

    Fitzpatrick, Benjamin L; Lau, Kai-Chung; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH(2)CHCH(2) radicals; these undergo a facile ring opening to the OCH(2)CHCH(2) radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcalmol. To elucidate the product channels resulting from the OCH(2)CHCH(2) radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C(3)H(4)O (acrolein)+H, C(2)H(4)+HCO (formyl radical), and H(2)CO (formaldehyde)+C(2)H(3). A small signal from C(2)H(2)O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at me=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C(2)H(5)+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  12. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, Benjamin L.; Lau, Kai-Chung; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim-Min, Jr.

    2008-08-01

    These experiments study the preparation of and product channels resulting from OCH2CHCH2, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH2CHCH2 radicals; these undergo a facile ring opening to the OCH2CHCH2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH2CHCH2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C3H4O (acrolein)+H, C2H4+HCO (formyl radical), and H2CO (formaldehyde)+C2H3. A small signal from C2H2O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C2H5+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to each of these product channels

  13. Hydrogen isotope systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis

    NASA Astrophysics Data System (ADS)

    Kobayashi, M.; Kawagucci, S.; Hattori, S.; Yamada, K.; Ueno, Y.; Takai, K.; Yoshida, N.

    2011-12-01

    Hydrogen and carbon isotopes of CH4 have been utilized to trace microbial processes. The isotope fractionations during hydrogenotrophic methanogenesis, one of the major processes of environmental CH4, have been studied by several laboratory incubations. For the carbon isotope, H2 concentration is thought to be the major parameter controlling the carbon isotope fractionation by hydrogenotrophic methanogenesis. For the hydrogen, on the other hand, factors controlling isotope fractionation remain poorly understood, although H2 concentration is suggested to be important. This uncertainty prevents us to utilize δD-CH4 value as the tracer. The most important and principal question is whether all hydrogen atoms in microbially-generated CH4 come from environmental H2O or not. To answer the question, we investigated the D/H systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis by pure culture incubation with softly deuterium-enriched H2 and/or H2O. Our results demonstrate that δD-CH4 value produced by hydrogenotrophic methanogens depends not only on δD-H2O value but also on δD-H2 value. We observed constant correlation between δD-H2 and δD-CH4 values as well as between δD-H2O and δD-CH4 values, which suggests that hydrogen (/deuterium) atom of substrate H2 is also transferred to the product CH4. This implies that the range of δD-CH4 value produced by hydrogenotrophic methanogenesis should be re-evaluated considering the distribution of δD-H2 and δD-H2O values in natural environments.

  14. Crystal and molecular structures of the first trans-macro-ansa monocyclophosphazene macrocycle, trans-N 3P 3Cl 4 [HN-(CH 2) 3-O-(CH 2) 6-O-(CH 2) 3-NH

    NASA Astrophysics Data System (ADS)

    Zanin, Bruno; Sournies, François; Labarre, Jean-François; Enjalbert, Renée; Galy, Jean

    1990-11-01

    The reaction of N 3P 3Cl 6 with 4,11-dioxatetradecane-1,14-diamine (designated 3O6O3) in a heterogeneous medium (interface process) of toluene and saturated aqueous Na 2CO 3 leads stereoselectively to a trans monocyclophosphazene 19-crown-ether species ( trans MACRO-ANSA 3O6O3) which crystallizes in the monoclinic system, P2 1/ na=8.539(2), b=8.997(3), c=30.123(4) Å, β=91.65(2)°, V=2313(2) Å 3, Z=4, Dx=1.456 Mg m -3, R=0.054 for 2826 unique reflections and 236 variable parameters. The structure exhibits a spatial arrangement with one [HN-(CH 2) 3-O-(CH 2) 6-O-(CH 2) 3-NH] as an arch, grafted in a trans configuration onto two different phosphorus atoms ( trans non-gem disubstitution) of one N 3P 3Cl 4 moiety. This fortuitously discovered trans-19-crown-ether-shaped macrocyclic structure defies the well-established description of the electronic structure of six-membered cyclophosphazene rings.

  15. Long persistent near infrared luminescence nanoprobes LiGa5O8:Cr3+-PEG-OCH3 for in vivo imaging

    NASA Astrophysics Data System (ADS)

    Fu, Xiaoyan; Liu, Chunlin; Shi, Junpeng; Man, Huizi; Xu, Jia; Zhang, Hongwu

    2014-09-01

    The Cr3+-doped LiGa5O8 nanoparticles (LGNPs) with long-persistent near-infrared phosphorescence were obtained through a sol-gel approach followed by heat treatment at 800 °C in air. The obtained results reveal that the nanoparticles with an average diameter of 100 nm are well defined and have pure structure of LiGa5O8. After illumination for 3 min using a 254 nm UV lamp, the LGNPs exhibit strong near-infrared peak at ca. 720 nm belonging to tissue transparency window which can last for more than 1 h. Via surface modified with PEG-5000-OCH3, the LGNPs-PEG-OCH3 exhibit excellent biocompatibility and low toxicity. Under in vitro pre-excitation using a 254 nm UV lamp for 3 min, the in vivo distribution of the LGNPs-PEG-OCH3 in the abdomen can be detected in real time for more than 1 h. All the results indicate that the LGNPs-PEG-OCH3 can be used as potential nanoprobes to realize in vivo, real time and long time imaging with high sensitivity.

  16. Induction of apoptosis in human mitogen-activated peripheral blood T-lymphocytes by the ether phospholipid ET-18-OCH3: Involvement of the Fas receptor/ligand system

    PubMed Central

    Cabaner, Christelle; Gajate, Consuelo; Macho, Antonio; Muñoz, Eduardo; Modolell, Manuel; Mollinedo, Faustino

    1999-01-01

    Activated T-cells constitute a target for treatment of autoimmune diseases. We have found that the antitumour ether phospholipid 1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine (ET-18-OCH3; edelfosine) induced dose- and time-dependent apoptosis in human mitogen-activated peripheral blood T-lymphocytes, but not in resting T-cells. T-lymphocytes were stimulated with phytohemagglutinin and interleukin-2 or with concanavalin A. Apoptosis was assessed by DNA fragmentation through cell cycle and TUNEL analyses, as well as through visualization of internucleosomal DNA fragmentation in agarose gels.The ET-18-OCH3-mediated apoptotic response in activated T-lymphocytes was less intense than in human leukaemic T cell lines, such as Jurkat cells and Peer cells; namely about 25% apoptosis in activated T-cells versus about 46–61% apoptosis in T leukaemic cells after 24 h treatment with 10 μM ET-18-OCH3.The ET-18-OCH3 thioether analogue BM 41.440 (ilmofosine) showed a similar apoptotic capacity to that found with ET-18-OCH3 in activated T-cells, whereas the phospholipid analogue hexadecylphosphocholine (miltefosine) failed to promote this response.The uptake of [3H]-ET-18-OCH3 was much larger in activated T-cells than in resting lymphocytes.Using a cytofluorimetric approach we have found that ET-18-OCH3 induced disruption of the mitochondrial transmembrane potential and production of reactive oxygen species in activated T-cells, but not in resting lymphocytes.ET-18-OCH3 induced an increase in Fas (APO-1/CD95) ligand mRNA expression in activated T-cells, and incubation with a blocking anti-Fas (APO-1/CD95) antibody partially inhibited the ET-18-OCH3-induced apoptosis of activated T-lymphocytes.These results demonstrate that mitogen-activated T-cells, unlike resting lymphocytes, are able to take up significant amounts of ET-18-OCH3, and are susceptible to undergo apoptosis by the ether lipid via, in part, the Fas (APO-1/CD95) receptor/ligand system. This ET-18-OCH3

  17. Characterization of Cu(II) and Cd(II) resistance mechanisms in Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and their potential application in the bioremediation of heavy metal-phenanthrene co-contaminated sites.

    PubMed

    Chen, Chen; Lei, Wenrui; Lu, Min; Zhang, Jianan; Zhang, Zhou; Luo, Chunling; Chen, Yahua; Hong, Qing; Shen, Zhenguo

    2016-04-01

    Soil that is co-contaminated with heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) is difficult to bioremediate due to the ability of toxic metals to inhibit PAH degradation by bacteria. We demonstrated the resistance mechanisms to Cu(II) and Cd(II) of two newly isolated strains of Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and further tested their potential application in the bioremediation of HM-phenanthrene (PhA) co-contaminated sites. The PHE-SPH and PHE-OCH strains tolerated 4.63 and 4.34 mM Cu(II) and also showed tolerance to 0.48 and 1.52 mM Cd(II), respectively. Diverse resistance patterns were detected between the two strains. In PHE-OCH cells, the maximum accumulation of Cu(II) occurred in the cell wall, while the maximum accumulation was in the cytoplasm of PHE-SPH cells. This resulted in a sudden suppression of growth in PHE-OCH and a gradual inhibition in PHE-SPH as the concentration of Cu(II) increased. Organic acid production was markedly higher in PHE-OCH than in PHE-SPH, which may also have a role in the resistance mechanisms, and contributes to the higher Cd(II) tolerance of PHE-OCH. The factors involved in the absorption of Cu(II) or Cd(II) in PHE-SPH and PHE-OCH were identified as proteins and carbohydrates by Fourier transform infrared (FT-IR) spectroscopy. Furthermore, both strains showed the ability to efficiently degrade PhA and maintained this high degradation efficiency under HM stress. The high tolerance to HMs and the PhA degradation capacity make Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH excellent candidate organisms for the bioremediation of HM-PhA co-contaminated sites.

  18. A single-molecule magnet featuring a parallelogram [Dy4(OCH2-)4] core and two magnetic relaxation processes.

    PubMed

    Liu, Cai-Ming; Zhang, De-Qing; Zhu, Dao-Ben

    2013-10-01

    An alkoxido-bridged tetranuclear Dy(iii) complex, [Dy4(H3L)2(OAc)6]·2EtOH {, H6L = 1,3-bis[tris(hydroxymethyl)methylamino]propane}, has been solvothermally synthesized and characterized. An X-ray crystallographic study revealed that complex possesses a novel "parallelogram" [Dy4(OCH2-)4] core, and a new binding mode η(3):η(3):η(1):η(1):η(1):η(2):μ(4) of the Bis-tris propane ligand was observed. Magnetic investigations indicated that it is a single-molecule magnet (SMM), showing two distinct magnetic relaxation processes with the energy barriers of 44 K and 107 K, respectively. Such a two-step magnetic relaxation process could be well described by the sum of two modified Debye functions.

  19. Disruption of the OCH1 and MNN1 genes decrease N-glycosylation on glycoprotein expressed in Kluyveromyces lactis.

    PubMed

    Liu, Bo; Gong, Xin; Chang, Shaohong; Yang, Yili; Song, Miao; Duan, Demin; Wang, Lina; Ma, Qingjun; Wu, Jun

    2009-08-20

    Glycoproteins secreted by the yeast Kluyveromyces lactis are usually modified by the addition at asparagines-linked glycosylation sites of heterogeneous mannan residues. The secreted glycoproteins in K. lactis that become hypermannosylated will bear a non-human glycosylation pattern and can adversely affect the half-life, tissue distribution and immunogenicity of a therapeutic protein. Here, we describe engineering a K. lactis strain to produce non-hypermannosylated glycoprotein, decreasing the outer-chain mannose residues of N-linked oligosaccharides. We investigated and developed the method of two-step homologous recombination to knockout the OCH1 gene, encoding alpha1,6-mannosyltransferase and MNN1 gene, which is homologue of Saccharomyces cerevisiae MNN1, encoding a putative alpha1,3-mannosyltransferase. We found the Kloch1 mutant strain has a defect in hyperglycosylation, inability in adding mannose to the core oligosaccharide. The N-linked oligosaccharides assembled on a secretory glycoprotein, HSA/GM-CSF in Kloch1 mutant, contained oligosaccharide Man(13-14)GlcNAc(2), and in Kloch1 mnn1 mutant, contained oligosaccharide Man(9-11)GlcNAc(2), whereas those in the wild-type strain, consisted of oligosaccharides with heterogeneous sizes, Man(>30)GlcNAc(2). Taken together, these results indicated that KlOch1p plays a key role in the outer-chain mannosylation of N-linked oligosaccharides in K. lactis. The KlMnn1p, was proved to be certain contribution to the outer hypermannosylation, most possibly encodes alpha1,3-mannosyltransferase. Therefore, the Kloch1 and Kloch1 mnn1 mutants can be used as a foundational host to produce glycoproteins lacking the outer-chain hypermannoses and further maybe applicable to be a promising system for yeast therapeutic protein production.

  20. Damage by radicals and photons during plasma cleaning of porous low-k SiOCH. II. Water uptake and change in dielectric constant

    SciTech Connect

    Shoeb, Juline; Kushner, Mark J.

    2012-07-15

    Porous dielectric materials provide lower capacitances that reduce RC time delays in integrated circuits. Typical low-k materials include porous SiOCH-silicon dioxide with carbon groups, principally CH{sub 3}, lining the pores. With a high porosity, internally connected pores provide pathways for reactive species to enter into the material. Fluorocarbon plasmas are often used to etch SiOCH, a process that leaves a fluorocarbon polymer on the surface that must later be removed. During cleaning using Ar/O{sub 2} or He/H{sub 2} plasmas, reactions of radicals that diffuse into the SiOCH and photons that penetrate into the SiOCH can remove -CH{sub 3} groups. Due to its higher reactivity, cleaning with Ar/O{sub 2} plasmas removes more -CH{sub 3} groups than He/H{sub 2} plasmas, and so produce more free radical sites, such as -SiO{sub 2} Bullet (a -SiO{sub 2}-CH{sub 3} site with the -CH{sub 3} group removed).Upon exposure to humid air, these free radical sites can chemisorb H{sub 2}O to form hydrophilic Si-OH which can further physisorb H{sub 2}O through hydrogen bonding to form Si-OH(H{sub 2}O). With the high dielectric constant of water, even a small percentage of water uptake can significantly increase the effective dielectric constant of SiOCH. In this paper, we report on results from a computational investigation of the cleaning of SiOCH using Ar/O{sub 2} or He/H{sub 2} plasmas and subsequent exposure to humid air. The authors found that plasma cleaning with He/H{sub 2} mixtures produce less demethylation than cleaning with Ar/O{sub 2} plasmas, as so results in less water uptake, and a smaller increase in dielectric constant. The water that produces the increase in dielectric constant is roughly half chemisorbed and half physisorbed, the latter of which can be removed with mild heating. Sealing the pores with NH{sub 3} plasma treatment reduces water uptake and helps prevent the increase in dielectric constant.

  1. Design of peptides with alpha,beta-dehydro residues: pseudo-tripeptide N-benzyloxycarbonyl-DeltaLeu-L-Ala-L-Leu-OCH3.

    PubMed

    Makker, Jyoti; Dey, Sharmistha; Kumar, Pravindra; Singh, Tej P

    2002-04-01

    The title peptide N-benzyloxycarbonyl-DeltaLeu-L-Ala-L-Leu-OCH(3) [methyl N-(benzyloxycarbonyl)-alpha,beta-dehydroleucyl-L-alanyl-L-leucinate], C(24)H(35)N(3)O(6), was synthesized in the solution phase. The peptide adopts a type II' beta-turn conformation which is stabilized by an intramolecular 4 --> 1 N-H* * *O hydrogen bond. The crystal packing is stabilized by two intermolecular N-H* * *O hydrogen bonds.

  2. A Study of Structural Changes in Pressed Semiproducts from Aluminum Alloy V95ochT2 in the Range of Dark Spots

    NASA Astrophysics Data System (ADS)

    Shigapov, A. I.; Il'inkova, T. A.; Kuryntsev, S. V.; Petrova, E. P.

    2017-01-01

    Seven heats of alloy V95ochT2 are studied after a heat treatment imitating the conditions of the appearance of dark spots in the production process and anodic oxidizing (anodizing). The mechanical properties, the hardness, the structure, and the electrical conductivity of the alloy are determined. The causes and conditions of the appearance of dark spots are analyzed. The transparence of the film is shown to worsen upon formation of particles of second phase in the alloy.

  3. H{sub 2}/N{sub 2} plasma damage on porous dielectric SiOCH film evaluated by in situ film characterization and plasma diagnostics

    SciTech Connect

    Yamamoto, Hiroshi; Takeda, Keigo; Ishikawa, Kenji; Hori, Masaru; Ito, Masafumi; Sekine, Makoto; Kaminatsui, Takeshi; Hayashi, Hisataka; Sakai, Itsuko; Ohiwa, Tokuhisa

    2011-04-15

    This study investigates the mechanism of H{sub 2}/N{sub 2} plasma ashing damage of porous SiOCH films. Porous SiOCH films were treated by a H{sub 2}/N{sub 2} plasma using a 100-MHz capacitively coupled plasma etcher. The impact of ions, radicals, and vacuum ultraviolet radiation on the porous SiOCH films was investigated using in situ bulk analysis techniques such as spectroscopic ellipsometry and Fourier-transform infrared spectroscopy and ex situ film characterization techniques such as dynamic secondary ion mass spectrometry and x-ray photoelectron spectroscopy. In addition, plasma analysis including vacuum ultraviolet absorption spectroscopy was performed. The film characterization and plasma analysis show that the extraction of methyl by H radicals was enhanced by light while N radicals were responsible for inhibit the extraction of Si-CH{sub 3} bonds by forming nitride layer. The H{sub 2}/N{sub 2} plasma damage mechanism is discussed based on characterization of the film and plasma diagnostics.

  4. Structural analysis of HS(CD(2))(12)(O-CH(2)-CH(2))(6)OCH(3) monolayers on gold by means of polarization modulation infrared reflection absorption spectroscopy. progress of the reaction with bromine.

    PubMed

    Brand, Izabella; Nullmeier, Martina; Klüner, Thorsten; Jogireddy, Rajamalleswaramma; Christoffers, Jens; Wittstock, Gunther

    2010-01-05

    A self-assembled monolayer (SAM) on gold was formed with specifically perdeuterated hexaethylene glycol-terminated alkanethiol HS(CD(2))(12)(O-CH(2)-CH(2))(6)OCH(3) (D-OEG). The structure of the d-alkane and the oligoethylene glycol (OEG) parts of the molecule in a SAM was studied by means of polarization modulation infrared reflection absorption spectroscopy. The D-OEG monolayers are highly ordered and exist in a crystalline phase. The d-alkane chain adopts an all-trans conformation. Both, the d-alkane chain and long axis of the OEG part make an angle of 26.0 degrees +/- 1.5 degrees with respect to the surface normal, a value characteristic for the tilt of solid n-alkane thiols in the SAMs on Au. The positions of nu(as)(COC) and CH(2) wagging and rocking modes indicate a helical arrangement of the OEG chains. The D-OEG SAMs were exposed to 25 muM Br(2) in two ways: (i) by immersion into the Br(2) solution and (ii) in the galvanic cell Au|D-OEG SAM|25 muM Br(2) + 0.1 M Na(2)SO(4)|| 50 muM KBr + 0.1 M Na(2)SO(4)|Au. In the galvanic cell, the oxidant (Br(2)) is scavenged by a heterogeneous electron transfer reaction, slowing the reaction of D-OEG with Br(2). The slow progress of the reaction with Br(2) allowed us to draw conclusions about molecular rearrangements taking place during this reaction. The reaction with Br(2) starts on boundaries and/or defects present in the SAM. First, at the defect place, the alpha-C atom of the OEG chain reacts with Br(2) and the OEG part of the molecule is removed from the monolayer. In consequence an increase in disorder in the OEG part of the SAM is observed. The same mechanism of the reaction with Br(2) is applied for the d-dodecane alkanethiol part of the molecule. This reaction is slow, thus the order and the tilt of the hydrocarbon chain changes only a little during the reaction time.

  5. Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

    NASA Astrophysics Data System (ADS)

    Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

    2015-03-01

    ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

  6. The effect of VUV radiation from Ar/O2 plasmas on low-k SiOCH films

    NASA Astrophysics Data System (ADS)

    Lee, J.; Graves, D. B.

    2011-08-01

    The degradation of porous low-k materials, like SiOCH, under plasma processing continues to be a problem in the next generation of integrated-circuit fabrication. Due to the exposure of the film to many species during plasma treatment, such as photons, ions, radicals, etc, it is difficult to identify the mechanisms responsible for plasma-induced damage. Using a vacuum beam apparatus with a calibrated Xe vacuum ultraviolet (VUV) lamp, we show that 147 nm VUV photons and molecular O2 alone can damage these low-k materials. Using Fourier-transform infrared (FTIR) spectroscopy, we show that VUV/O2 exposure causes a loss of methylated species, resulting in a hydrophilic, SiOx-like layer that is susceptible to H2O absorption, leading to an increased dielectric constant. The effect of VUV radiation on chemical modification of porous SiOCH films in the vacuum beam apparatus and in Ar and O2 plasma exposure was found to be a significant contributor to dielectric damage. Measurements of dielectric constant change using a mercury probe are consistent with chemical modification inferred from FTIR analysis. Furthermore, the extent of chemical modification appears to be limited by the penetration depth of the VUV photons, which is dependent on wavelength of radiation. The creation of a SiOx-like layer near the surface of the material, which grows deeper as more methyl is extracted, introduces a dynamic change of VUV absorption throughout the material over time. As a result, the rate of methyl loss is continuously changing during the exposure. We present a model that attempts to capture this dynamic behaviour and compare the model predictions to experimental data through a fitting parameter that represents the effective photo-induced methyl removal. While this model accurately simulates the methyl loss through VUV exposure by the Xe lamp and Ar plasma, the methyl loss from VUV photons in O2 plasma are only accurately depicted at longer exposure times. We conclude that other

  7. Analysis of the kinetics and yields of OH radical production from the CH3OCH2 + O2 reaction in the temperature range 195-650 K: an experimental and computational study.

    PubMed

    Eskola, A J; Carr, S A; Shannon, R J; Wang, B; Blitz, M A; Pilling, M J; Seakins, P W; Robertson, S H

    2014-08-28

    The methoxymethyl radical, CH3OCH2, is an important intermediate in the low temperature combustion of dimethyl ether. The kinetics and yields of OH from the reaction of the methoxymethyl radical with O2 have been measured over the temperature and pressure ranges of 195-650 K and 5-500 Torr by detecting the hydroxyl radical using laser-induced fluorescence following the excimer laser photolysis (248 nm) of CH3OCH2Br. The reaction proceeds via the formation of an energized CH3OCH2O2 adduct, which either dissociates to OH + 2 H2CO or is collisionally stabilized by the buffer gas. At temperatures above 550 K, a secondary source of OH was observed consistent with thermal decomposition of stabilized CH3OCH2O2 radicals. In order to quantify OH production from the CH3OCH2 + O2 reaction, extensive relative and absolute OH yield measurements were performed over the same (T, P) conditions as the kinetic experiments. The reaction was studied at sufficiently low radical concentrations (∼10(11) cm(-3)) that secondary (radical + radical) reactions were unimportant and the rate coefficients could be extracted from simple bi- or triexponential analysis. Ab initio (CBS-GB3)/master equation calculations (using the program MESMER) of the CH3OCH2 + O2 system were also performed to better understand this combustion-related reaction as well as be able to extrapolate experimental results to higher temperatures and pressures. To obtain agreement with experimental results (both kinetics and yield data), energies of the key transition states were substantially reduced (by 20-40 kJ mol(-1)) from their ab initio values and the effect of hindered rotations in the CH3OCH2 and CH3OCH2OO intermediates were taken into account. The optimized master equation model was used to generate a set of pressure and temperature dependent rate coefficients for the component nine phenomenological reactions that describe the CH3OCH2 + O2 system, including four well-skipping reactions. The rate coefficients were

  8. Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

    USGS Publications Warehouse

    Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

    2013-01-01

    Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

  9. An organo-functionalized metal-oxide cluster, [VO6{(OCH2CH2)2N(CH2CH2OH)}6], with Anderson-like structure.

    PubMed

    Li, H; Swenson, L; Doedens, R J; Khan, M I

    2016-10-18

    A new polyoxovanadium cluster compound, [VO6{(OCH2CH2)2N(CH2CH2OH)}6]·0.5CH3CN, was synthesized and characterized by single-crystal X-ray diffraction analysis, FTIR and UV-vis spectroscopy, and TGA. The cluster is composed of a fully reduced cyclic {V6N6O18} framework, which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VO5N} octahedra incorporating six {(OCH2CH2)2N(CH2CH2OH)} ligands. Two (OCH2CH2-) arms of each of the six triethanolamine ligands are directly incorporated into the oxometalate core and the third {-CH2CH2OH} arm remains pendant. In the condensed phase, the clusters form discrete hcp layers through inter-cluster hydrogen bonding. These layers stack through soft chemical interactions to form a 3D network structure. The neutral cluster, [VO6{(OCH2CH2)2N(CH2CH2OH)}6], is the isopolyoxovanadium analogue to the cationic clusters contained in a series of heteropolyoxovanadium compounds previously introduced by our laboratory, e.g., [LiVO6{(OCH2CH2)2N(CH2CH2OH)}6](+); its existence shows that a heteroatom is not required to form or stabilize the common organofunctionalized vanadium oxide framework: [VO6{(OCH2CH2)2N(CH2CH2OH)}6]. To the best of our knowledge, the isopolyoxovanadium and heteropolyoxovanadium clusters represent the first reported isopoly-heteropoly analogues in the polyoxometalate field. We compare the TGA profile, FTIR and UV-vis spectra of the new compound with two of its cationic heteropoly analogues.

  10. The Cl-initiated oxidation of CH(3)C(O)OCH=CH (2), CH (3)C(O)OCH (2)CH=CH (2), and CH (2)=CHC(O)O(CH (2)) (3)CH (3) in the troposphere.

    PubMed

    Blanco, María B; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A

    2009-09-01

    Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 +/- 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate. The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds. The following room temperature rate coefficients (in cm(3) molecule(-1) s(-1)) were obtained: k (1) (Cl + CH(3)C(O)OCH=CH(2)) = (2.68 +/- 0.91) x 10(-10), k (2) (Cl + CH(3)C(O)OCH(2)CH=CH(2)) = (1.30 +/- 0.45) x 10(-10), and k (3) (Cl + CH(2)=CHC(O)O(CH(2))(3)CH(3)) = (2.50 +/- 0.78) x 10(-10), where the uncertainties are a combination of the 2sigma statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons. This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere. Although reaction with OH radicals

  11. A computational study of the addition of ReO3L (L = Cl(-), CH3, OCH3 and Cp) to ethenone.

    PubMed

    Aniagyei, Albert; Tia, Richard; Adei, Evans

    2016-01-01

    The periselectivity and chemoselectivity of the addition of transition metal oxides of the type ReO3L (L = Cl, CH3, OCH3 and Cp) to ethenone have been explored at the MO6 and B3LYP/LACVP* levels of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of ReO3L (L = Cl(-), OCH3, CH3 and Cp) with ethenone, the concerted [2 + 2] addition of the metal oxide across the C=C and C=O double bond to form either metalla-2-oxetane-3-one or metalla-2,4-dioxolane is the most kinetically favored over the formation of metalla-2,5-dioxolane-3-one from the direct [3 + 2] addition pathway. The trends in activation and reaction energies for the formation of metalla-2-oxetane-3-one and metalla-2,4-dioxolane are Cp < Cl(-) < OCH3 < CH3 and Cp < OCH3 < CH3 < Cl(-) and for the reaction energies are Cp < OCH3 < Cl(-) < CH3 and Cp < CH3 < OCH3 < Cl CH3. The concerted [3 + 2] addition of the metal oxide across the C=C double of the ethenone to form species metalla-2,5-dioxolane-3-one is thermodynamically the most favored for the ligand L = Cp. The direct [2 + 2] addition pathways leading to the formations of metalla-2-oxetane-3-one and metalla-2,4-dioxolane is thermodynamically the most favored for the ligands L = OCH3 and Cl(-). The difference between the calculated [2 + 2] activation barriers for the addition of the metal oxide LReO3 across the C=C and C=O functionalities of ethenone are small except for the case of L = Cl(-) and OCH3. The rearrangement of the metalla-2-oxetane-3-one-metalla-2,5-dioxolane-3-one even though feasible, are unfavorable due to high activation energies of their rate-determining steps. For the rearrangement of the metalla-2-oxetane-3-one to metalla-2,5-dioxolane-3-one, the trends in activation barriers is found to follow the order OCH3 < Cl(-) < CH3 < Cp. The trends in the activation energies for

  12. Investigation of the O+allyl addition/elimination reaction pathways from the OCH{sub 2}CHCH{sub 2} radical intermediate

    SciTech Connect

    FitzPatrick, Benjamin L.; Lau, K.-C.; Butler, Laurie J.; Lee, S.-H.; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH{sub 2}CHCH{sub 2}, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH{sub 2}CHCH{sub 2} radicals; these undergo a facile ring opening to the OCH{sub 2}CHCH{sub 2} radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH{sub 2}CHCH{sub 2} radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C{sub 3}H{sub 4}O (acrolein)+H, C{sub 2}H{sub 4}+HCO (formyl radical), and H{sub 2}CO (formaldehyde)+C{sub 2}H{sub 3}. A small signal from C{sub 2}H{sub 2}O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C{sub 2}H{sub 5}+CO, does not contribute significantly to the product branching. The higher internal energy onset of the

  13. Distribution of eukaryotic serine racemases in the bacterial domain and characterization of a representative protein in Roseobacter litoralis Och 149.

    PubMed

    Kubota, Takaaki; Shimamura, Shigeru; Kobayashi, Tohru; Nunoura, Takuro; Deguchi, Shigeru

    2016-01-01

    Two distinct bacterial and eukaryotic serine racemases (SRs) have been identified based on phylogenetic and biochemical characteristics. Although some reports have suggested that marine heterotrophic bacteria have the potential to produce d-serine, the gene encoding bacterial SRs is not found in those bacterial genomes. In this study, using in-depth genomic analysis, we found that eukaryotic SR homologues were distributed widely in various bacterial genomes. Additionally, we selected a eukaryotic SR homologue from a marine heterotrophic bacterium, Roseobacter litoralis Och 149 (RiSR), and constructed an RiSR gene expression system in Escherichia coli for studying the properties of the enzyme. Among the tested amino acids, the recombinant RiSR exhibited both racemization and dehydration activities only towards serine, similar to many eukaryotic SRs. Mg2+ and MgATP enhanced both activities of RiSR, whereas EDTA abolished these enzymatic activities. The enzymatic properties and domain structure of RiSR were similar to those of eukaryotic SRs, particularly mammalian SRs. However, RiSR showed lower catalytic efficiency for L-serine dehydration (kcat/Km=0.094 min(-1) mM(-1)) than those of eukaryotic SRs reported to date (kcat/Km=0.6-21 min(-1) mM(-1)). In contrast, the catalytic efficiency for L-serine racemization of RiSR (kcat/Km=3.14 min(-1) mM(-1)) was 34-fold higher than that of l-serine dehydration. These data suggested that RiSR primarily catalysed serine racemization rather than dehydration.

  14. The H2O-CH3F Complex: a Combined Microwave and Infrared Spectroscopic Study Supported by Structure Calculations

    NASA Astrophysics Data System (ADS)

    Gnanasekar, Sharon Priya; Goubet, Manuel; Arunan, Elangannan; Georges, Robert; Soulard, Pascale; Asselin, Pierre; Huet, T. R.; Pirali, Olivier

    2015-06-01

    The H2O-CH3F complex could have two geometries, one with a hydrogen bond and one with the newly proposed carbon bond. While in general carbon bonds are weaker than hydrogen bonds, this complex appears to have comparable energies for the two structures. Infrared (IR) and microwave (MW) spectroscopic measurements using, respectively, the Jet-AILES apparatus and the FTMW spectrometer at the PhLAM laboratory, have been carried out to determine the structure of this complex. The IR spectrum shows the formation of the CH3F- H2O hydrogen bonded complex and small red-shifts in OH frequency most probably due to (CH3F)m-(H2O)n clusters. Noticeably, addition of CH_3F in the mixture promotes the formation of small water clusters. Preliminary MW spectroscopic measurements indicate the formation of the hydrogen bonded complex. So far, we have no experimental evidence for the carbon bonded structure. However, calculations of the Ar-CH3F complex show three energetically equivalent structures: a T-shape, a "fluorine" bond and a carbon bond. The MW spectrum of the (Ar)n-CH3F complexes is currently under analysis. Mani, D; Arunan, E. Phys. Chem. Chem. Phys. 2013, 15, 14377. Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebene, B; Alikhani, M. E; Georges, R; Moudens, A; Goubet, M; Huet, T.R; Pirali, O; Roy, P. J. Phys. Chem. A. 2011, 115, 2523 Kassi, S; Petitprez, D; Wlodarczak, G. J. Mol. Struct. 2000, 517-518, 375

  15. The remarkable dissociation chemistry of 2-aminoxyethanol ions NH2OCH2CH2OH+studied by experiment and theory

    NASA Astrophysics Data System (ADS)

    Jobst, Karl J.; Ruttink, Paul J. A.; Terlouw, Johan K.

    2008-02-01

    Low-energy 2-aminoxyethanol molecular ions NH2OCH2CH2OH+ exhibit a surprisingly rich gas-phase ion chemistry. They spontaneously undergo five major dissociations in the microsecond timeframe, yielding ions of m/z 61, 60, 46, 32 and 18. Our tandem mass spectrometry experiments indicate that these reactions correspond to the generation of HOCH2CH(OH)+ (protonated glycolaldehyde), HOCH2C(O)H+ (ionized glycolaldehyde), HC(OH)NH2+ (protonated formamide), CH2OH2+ (the methylene oxonium ion) and NH4+. A mechanistic analysis of these processes using the CBS-QB3 model chemistry shows that the molecular ions undergo a 1,4-H shift followed by a facile isomerization into the ion-molecule complex [HOCH2C(O)H+]...[NH3] which acts as the reacting configuration for the five exothermic dissociation processes. Analysis of the D-labelled isotopomer ND2OCH2CH2OD+, in conjunction with our computational results, shows that proton-transport catalysis may be responsible for the partial conversion of the m/z 60 glycolaldehyde ions into the more stable 1,2-dihydroxyethene isomer HOC(H)C(H)OH+.

  16. A DFT study on the functionalization of a BN nanosheet with PCsbnd X, (PC = phenyl carbamate, X = OCH3, CH3, NH2, NO2 and CN)

    NASA Astrophysics Data System (ADS)

    Beheshtian, Javad; Soleymanabadi, Hamed; Peyghan, Ali Ahmadi; Bagheri, Zargham

    2013-03-01

    By using density functional theory calculations, we investigated the chemical functionalization of a BN nanosheet with different organo-azo derivatives including PCsbnd X, (PC = phenyl carbamate, X = OCH3, CH3, NH2, NO2 and CN) in terms of geometric, energetic, and electronic properties. Reaction energies have been calculated to be in the range of 0.19 to 0.35 eV which is augmented by increasing the electron withdrawing characteristic of the functional groups so that the relative magnitude order is sbnd NO2 > sbnd CN > sbnd OCH3 > sbnd CH3 > sbnd NH2. The chemical functionalization leads to a decrease in HOMO/LUMO energy gap of BN sheet especially after adsorption of PCsbnd NO2 by about 1.88 eV. Conduction level and Fermi level of the BN sheet are shifted to lower energies upon the functionalization of the sheet with PCsbnd NO2 and PCsbnd CN, thus, it leads to an increment in work function of the sheet, impeding the field electron emission.

  17. Isoelectronic caesium compounds: the triphosphenide Cs[tBu3SiPPPSitBu3] and the enolate Cs[OCH=CH2].

    PubMed

    Lerner, Hans-Wolfram; Sänger, Inge; Schödel, Frauke; Lorbach, Andreas; Bolte, Michael; Wagner, Matthias

    2008-02-14

    The caesium triphosphenide Cs[tBu3SiPPPSitBu3] was accessible from the reaction of CsF with the sodium triphosphenide Na[tBu3SiPPPSitBu3] in tetrahydrofuran at room temperature. In contrast to the preparation of tetrahydrofuran-solvated silanides M[SitBu3] (M = Li, Na, K), our efforts to synthesize the caesium silanide Cs[SitBu3] as a tetrahydrofuran complex failed. When tBu3SiBr was treated with an excess of caesium metal in tetrahydrofuran at room temperature, the caesium enolate Cs[OCH=CH2] and the supersilane tBu3SiH formed rather than the silanide Cs[SitBu3]. X-Ray quality crystals of the enolate Cs[OCH=CH2] (orthorhombic, Pnma) were obtained from tetrahydrofuran at ambient temperature. In contrast to the structures of its homologues M[tBu3SiPPPSitBu3] (M = Na, K), the caesium triphosphenide Cs[tBu3SiPPPSitBu3] features a polymer in the solid state (orthorhombic, Cmcm).

  18. Impact of Hydrocarbon Control in Ultraviolet-Assisted Restoration Process for Extremely Porous Plasma Enhanced Chemical Vapor Deposition SiOCH Films with k = 2.0

    NASA Astrophysics Data System (ADS)

    Kimura, Yosuke; Ishikawa, Dai; Nakano, Akinori; Kobayashi, Akiko; Matsushita, Kiyohiro; de Roest, David; Kobayashi, Nobuyoshi

    2012-05-01

    We investigated the effects of UV-assisted restoration on porous plasma-enhanced chemical vapor deposition (PECVD) SiOCH films with k = 2.0 and 2.3 having high porosities. By applying the UV-assisted restoration to O2-plasma-damaged films with k = 2.0 and 2.3, the recovery of the k-value was observed on the k = 2.3 film in proportion to -OH group reduction. However, the k = 2.0 film did not show recovery in spite of -OH group reduction. We found that hydrocarbon content in the k = 2.0 film was significantly increased by the UV-assisted restoration compared with the k = 2.3 film. According to these findings, we optimized the UV-assisted restoration to achieve improved controllability of the hydrocarbon uptake in the k = 2.0 film and confirmed the recovery of the k-value for O2-plasma-damaged film. Thus, adjusting the hydrocarbon uptake was crucial for restoring extremely porous SiOCH film.

  19. Theoretical investigation on the atmospheric fate of CF3C(O)OCH 2O radical: alpha-ester rearrangement vs oxidation at 298 K.

    PubMed

    Mishra, Bhupesh Kumar

    2014-09-01

    A theoretical study on the mechanism of the thermal decomposition of CF(3)C(O)OCH(2)O radical is presented for the first time. Geometry optimization and frequency calculations were performed at the MPWB1K/6-31 + G(d, p) level of theory and energetic information further refined by calculating the energy of the species using G2(MP2) theory. Three plausible decomposition pathways including α-ester rearrangement, reaction with O(2) and thermal decomposition (C-O bond scission) were considered in detail. Our results reveal that reaction with O(2) is the dominant path for the decomposition of CF(3)C(O)OCH(2)O radical in the atmosphere, involving the lowest energy barrier, which is in accord with experimental findings. Our theoretical results also suggest that α-ester rearrangement leading to the formation of trifluoroacetic acid TFA makes a negligible contribution to decomposition of the title alkoxy radical. The thermal rate constants for the above decomposition pathways were evaluated using canonical transition state theory (CTST) at 298 K.

  20. An extended π-system and enhanced electronic delocalization on symmetric [Ru3O(CH3COO)6(L)3](n) complexes combined with azanaphthalene ligands.

    PubMed

    Possato, Bruna; Deflon, Victor M; Naal, Zeki; Formiga, André L B; Nikolaou, Sofia

    2017-06-28

    We report on the investigation of a new series of symmetric trinuclear ruthenium complexes combined with azanaphthalene ligands: [Ru3O(CH3COO)6(L)3]PF6 where L = (1) quinazoline (qui), (2) 5-nitroisoquinoline (5-nitroiq), (3) 5-bromoisoquinoline (5-briq), (4) isoquinoline (iq), (5) 5-aminoisoquinoline (5-amiq), and (6) 5,6,7,8-tetrahydroisoquinoline (thiq). The crystal structure of complex 1, [Ru3O(CH3COO)6(qui)3]PF6, was determined by X-ray diffraction analysis, showing a high degree of co-planarity between the [Ru3O] plane and the azanaphthalene ligands. Spectroscopic (UV-visible, NMR and infra-red) and electrochemical (cyclic voltammetry and spectroelectrochemistry) data showed correlation with the pKa values of the azanaphthalene ligands and this dependence was rationalized in terms of the molecular orbital of the [Ru3O] unit and the structure of the ligands. By analysing the spectroscopic and electrochemical correlations, the ability of the azanaphthalene ligands to extend the electronic π-system of the [Ru3O] unit to the periphery of the compounds was demonstrated. This electronic effect accounts for the planarity of the structure of complex 1. It was also shown through molecular modeling results that, to explain the spectroscopic and electrochemical behaviour of these species, it is not possible to neglect the electronic mixing between the metallic and the acetate orbitals. Finally, this work revealed that electronic coupling is more pronounced in the azanaphthalene series of complexes than in pyridinic analogues and it is this coupling that determines the spectroscopic and electrochemical behaviour of the new species.

  1. Chiral and nonchiral [OsX2(diphosphane)(diamine)] (X: Cl, OCH2CF3) complexes for fast hydrogenation of carbonyl compounds.

    PubMed

    Baratta, Walter; Barbato, Cinzia; Magnolia, Santo; Siega, Katia; Rigo, Pierluigi

    2010-03-08

    The osmium complexes trans-[OsCl(2)(dppf)(diamine)] (dppf: 1,1'-bis(diphenylphosphino)ferrocene; diamine: ethylenediamine in 3, propylenediamine in 4) were prepared by the reaction of [OsCl(2)(PPh(3))(3)] (1) with the ferrocenyl diphosphane, dppf and the corresponding diamine in dichloromethane. The reaction of derivative 3 with NaOCH(2)CF(3) in toluene afforded the alkoxide cis-[Os(OCH(2)CF(3))(2)(dppf)(ethylenediamine)] (5). The novel precursor [Os(2)Cl(4)(P(m-tolyl)(3))(5)] (2) allows the synthesis of the chiral complexes trans-[OsCl(2)(diphosphane)(1,2-diamine)] (6-9; diphosphane: (R)-[6,6'-dimethoxy(1,1'-biphenyl)-2,2'-diyl]bis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylMeObiphep) or (R)-(1,1'-binaphthalene)-2,2'-diylbis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylbinap); diamine=(R,R)-1,2-diphenylethylenediamine (dpen) or (R,R)-1,2-diaminocyclohexane (dach)), obtained by the treatment of 2 with the diphosphane and the 1,2-diamine in toluene at reflux temperature. Compounds 3-5 in ethanol and in the presence of NaOEt catalyze the reduction of methyl aryl, dialkyl, and diaryl ketones and aldehydes with H(2) at low pressure (5 atm), with substrate/catalyst (S/C) ratios of 10,000-200,000 and achieving turnover frequencies (TOFs) of up to 3.0 x 10(5) h(-1) at 70 degrees C. By employment of the chiral compounds 6-9, different ketones, including alkyl aryl, bulky tert-butyl, and cyclic ketones, have successfully been hydrogenated with enantioselectivities up to 99% and with S/C ratios of 5000-100,000 and TOFs of up to 4.1 x 10(4) h(-1) at 60 degrees C.

  2. Rotational Spectrum, Conformational Composition, and Quantum Chemical Calculations of Cyanomethyl Formate (HC(O)OCH2C≡N), a Compound of Potential Astrochemical Interest.

    PubMed

    Samdal, Svein; Møllendal, Harald; Carles, Sophie

    2015-08-27

    The rotational spectrum of cyanomethyl formate (HC(O)OCH2C≡N) has been recorded in the 12–123 GHz spectral range. The spectra of two conformers were assigned. The rotamer denoted I has a symmetry plane and two out-of plane hydrogen atoms belonging to the cyanomethyl (CH2CN) moiety. In the conformer called II, the cyanomethyl group is rotated 80.3° out of this plane. Conformer I has an energy that is 1.4(6) kJ/mol lower than the energy of II according to relative intensity measurements. A large number of rotational transitions have been assigned for the ground and vibrationally excited states of the two conformers and accurate spectroscopic constants have been obtained. These constants should predict frequencies of transitions outside the investigated spectral range with a very high degree of precision. It is suggested that cyanomethyl formate is a potential interstellar compound. This suggestion is based on the fact that its congener methyl formate (HC(O)OCH3) exists across a large variety of interstellar environments and the fact that cyanides are very prevalent in the Universe. The experimental work has been augmented by high-level quantum chemical calculations. The CCSD/cc-pVQZ calculations are found to predict structures of the two forms that are very close to the Born–Oppenheimer equilibrium structures. MP2/cc-pVTZ predictions of several vibration–rotation interaction constants were generally found to be rather inaccurate. A gas-phase reaction between methyl formate and the cyanomethyl radical CH2CN to produce a hydrogen atom and cyanomethyl formate was mimicked using MP2/cc-pVTZ calculations. It was found that this reaction is not favored thermodynamically. It is also conjectured that the possible formation of cyanomethyl formate might be catalyzed and take place on interstellar particles.

  3. Forskolebarn och TV.

    ERIC Educational Resources Information Center

    Sonesson, Inga

    This analysis of the relationship between mothers' attitudes toward TV and children's viewing habits, and the relationships between this behavior and the personal and/or social problems of the child, is based on data gathered in interviews with 250 preschool children, their mothers, and their teachers. Findings indicate a positive correlation…

  4. Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials.

    PubMed

    Bravo, Iván; Díaz-de-Mera, Yolanda; Aranda, Alfonso; Smith, Kevin; Shine, Keith P; Marston, George

    2010-05-21

    The atmospheric chemistry of several gases used in industrial applications, C(4)F(9)OC(2)H(5) (HFE-7200), C(4)F(9)OCH(3) (HFE-7100), C(3)F(7)OCH(3) (HFE-7000) and C(3)F(7)CH(2)OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm(3) molecule(-1) s(-1)): k(OH + HFE-7200) = (6.9(-1.7)(+2.3)) x 10(-11) exp(-(2030 +/- 190)/T); k(OH + HFE-7100) = (2.8(-1.5)(+3.2)) x 10(-11) exp(-(2200 +/- 490)/T); k(OH + HFE-7000) = (2.0(-0.7)(+1.2)) x 10(-11) exp(-(2130 +/- 290)/T); and k(OH + C(3)F(7)CH(2)OH) = (1.4(-0.2)(+0.3)) x 10(-11) exp(-(1460 +/- 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO(2) of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively.

  5. Dinuclear [(V(V)O(putrebactin))2(μ-OCH3)2] formed in solution as established from LC-MS measurements using 50V-enriched V2O5.

    PubMed

    Soe, Cho Zin; Pakchung, Amalie A H; Codd, Rachel

    2014-06-02

    Analysis of 1:1 solutions of V(V) and the macrocyclic dihydroxamic acid siderophore putrebactin (pbH2) in 1:1 H2O/CH3OH using triple quadrupole liquid chromatography-mass spectrometry (LC-MS-QQQ) (pH ≈ 4) showed two well-resolved peaks (tR(1) 10.85 min; tR(2) 14.27 min) using simultaneous detection modes (absorbance, 450 nm; selective ion monitoring, m/z 437) characteristic of the previously identified oxidoV(V) complex [V(V)O(pb)](+) ([M](+), m/zcalc 437.1). Peak 1 gave mass spectrometry (MS) signals consistent with [V(V)O(pb)](+), together with [V(V)O(pb)(OH)] and the dinuclear complexes [(V(V)O(pb))2(μ-OH)](+) and [(V(V)O(pb))2(μ-OH)2]. Peak 2 gave MS signals consistent with [V(V)O(pb)](+), together with [V(V)O(pb)(OCH3)] and the dinuclear complexes [(V(V)O(pb))2(μ-OCH3)](+) and [(V(V)O(pb))2(μ-OCH3)2]. This analysis showed that two groups of V(V)/pbH2 complexes with water- or methanol-derived ancillary ligands were resolved by liquid chromatography (LC). The detection of [V(V)O(pb)](+) in both peaks could be accounted for by its production from dissociation (peak 1: [(V(V)O(pb))2(μ-OH)](+) → [V(V)O(pb)](+) + [V(V)O(pb)(OH)]; peak 2: [(V(V)O(pb))2(μ-OCH3)](+) → [V(V)O(pb)](+) + [V(V)O(pb)(OCH3)]). The assignment of the signal at m/zobs 959.2 (100%) as the dinuclear complex [(V(V)O(pb))2(μ-OCH3)2] ([M + Na(+)](+), m/zcalc 959.3) and not an ion cluster of mononuclear [V(V)O(pb)(OCH3)] ({2[M] + Na(+)}(+), m/zcalc 959.3) was made unequivocal by the use of (50)V-enriched V2O5, which gave a signal with an isotope pattern comprising the sum of the patterns of the three constituent (51)V-(51)V, (51)V-(50)V, and (50)V-(50)V species. Coordination of methoxide was confirmed upon the replacement of CH3OH with CD3OD, which generated [(V(V)O(pb))2(μ-OCD3)2] ([M + Na(+)](+), m/zcalc 965.3, m/zobs 965.3). Analysis of 1:1 solutions of Mo(VI) and pbH2 showed a single peak in the LC (tR 16.04 min), which gave MS signals that were characterized as mononuclear [Mo

  6. Evaluation of a Novel Approach for Peptide Sequencing: Laser-induced Acoustic Desorption Combined with P(OCH3)2+ Chemical Ionization and Collision-activated Dissociation in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    PubMed Central

    Somuramasami, Jayalakshmi; Kenttämaa, Hilkka I.

    2007-01-01

    A novel mass spectrometric method has been developed for obtaining sequence information on small peptides. The peptides are desorbed as intact neutral molecules into a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) by means of laser-induced acoustic desorption (LIAD). Reactions of the neutral peptides with the dimethoxyphosphenium ion, P(OCH3)2+, occur predominantly by addition of the peptide to P(OCH3)2+ followed by the loss of two methanol molecules, thus yielding product ions with the composition (peptide + P − 2H)+. Upon sustained off-resonance irradiation for collision-activated dissociation (SORI-CAD), the (peptide + P − 2H)+ ions undergo successive losses of CO and NH = CHR or H2O, CO, and NH = CHR to yield sequence-related fragment ions in addition to the regular an- and bn-type ions. Under the same conditions, SORI-CAD of the analogous protonated peptides predominantly yields the regular an- and bn-type ions. The mechanisms of the reactions of peptides with P(OCH3)2+ and the dissociation of the (peptide + P − 2H)+ ions were examined by using model peptides and molecular orbital calculations. PMID:17157527

  7. Evaluation of a novel approach for peptide sequencing: laser-induced acoustic desorption combined with P(OCH(3))(2)(+) chemical ionization and collision-activated dissociation in a Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Somuramasami, Jayalakshmi; Kenttämaa, Hilkka I

    2007-03-01

    A novel mass spectrometric method has been developed for obtaining sequence information on small peptides. The peptides are desorbed as intact neutral molecules into a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) by means of laser-induced acoustic desorption (LIAD). Reactions of the neutral peptides with the dimethoxyphosphenium ion, P(OCH(3))(2)(+), occur predominantly by addition of the peptide to P(OCH(3))(2)(+) followed by the loss of two methanol molecules, thus yielding product ions with the composition (peptide + P - 2H)(+). Upon sustained off-resonance irradiation for collision-activated dissociation (SORI-CAD), the (peptide + P - 2H)(+) ions undergo successive losses of CO and NHCHR or H(2)O, CO, and NHCHR to yield sequence-related fragment ions in addition to the regular a(n)- and b(n)-type ions. Under the same conditions, SORI-CAD of the analogous protonated peptides predominantly yields the regular a(n)- and b(n)-type ions. The mechanisms of the reactions of peptides with P(OCH(3))(2)(+) and the dissociation of the (peptide + P - 2H)(+) ions were examined by using model peptides and molecular orbital calculations.

  8. Global Uncertainty Propagation and Sensitivity Analysis in the CH3OCH2 + O2 System: Combining Experiment and Theory To Constrain Key Rate Coefficients in DME Combustion.

    PubMed

    Shannon, R J; Tomlin, A S; Robertson, S H; Blitz, M A; Pilling, M J; Seakins, P W

    2015-07-16

    Statistical rate theory calculations, in particular formulations of the chemical master equation, are widely used to calculate rate coefficients of interest in combustion environments as a function of temperature and pressure. However, despite the increasing accuracy of electronic structure calculations, small uncertainties in the input parameters for these master equation models can lead to relatively large uncertainties in the calculated rate coefficients. Master equation input parameters may be constrained further by using experimental data and the relationship between experiment and theory warrants further investigation. In this work, the CH3OCH2 + O2 system, of relevance to the combustion of dimethyl ether (DME), is used as an example and the input parameters for master equation calculations on this system are refined through fitting to experimental data. Complementing these fitting calculations, global sensitivity analysis is used to explore which input parameters are constrained by which experimental conditions, and which parameters need to be further constrained to accurately predict key elementary rate coefficients. Finally, uncertainties in the calculated rate coefficients are obtained using both correlated and uncorrelated distributions of input parameters.

  9. Investigating the H2-He-H2O-CH4 equation of state in the deep troposphere of Jupiter

    NASA Astrophysics Data System (ADS)

    Karpowicz, Bryan M.; Steffes, Paul G.

    2013-03-01

    In this work, a new equation of state for a H2-He-H2O-CH4 mixture is presented. The equation is optimized for the deep jovian atmosphere (∼100 bars) where the NASA Juno Microwave Radiometer (MWR) will probe. The methodology used is based upon that of Lemmon and Jacobsen (Lemmon, E.W., Jacobsen, R.T. [2004]. J. Phys. Chem. Ref. Data 33, 593-+) and Kunz et al. (Kunz, O., Klimeck, R., Wagner, W., Jaeschke, M. [2006]. Technical Monograph, VDI-Verlag). This methodology is used in combination with available published thermodynamic measurements and with new pressure-Volume-Temperature (pVT) measurements of H2-H2O mixtures conducted with the jovian simulator described in Karpowicz and Steffes (Karpowicz, B.M., Steffes, P.G. [2011]. Icarus 212, 210-223). In addition to being necessary to interpret laboratory measurements, the new equation of state is important in developing temperature pressure profiles of the deep jovian atmosphere. This is demonstrated by incorporating the new equation of state into an updated version of the DeBoer (DeBoer, D.R. [1995]. Ph.D. Thesis, Georgia Institute of Technology) Thermo-Chemical Model (TCM), and viewing its effect on the resulting simulated jovian atmospheric profiles.

  10. H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations.

    PubMed

    Cappelletti, David; Bartocci, Alessio; Frati, Federica; Roncaratti, Luiz F; Belpassi, Leonardo; Tarantelli, Francesco; Lakshmi, Prabha Aiswarya; Arunan, Elangannan; Pirani, Fernando

    2015-11-11

    New molecular beam scattering experiments have been performed to measure the total (elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as 'hydrogen bonded'.

  11. On the Formation of the C2H6O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming Regions

    NASA Astrophysics Data System (ADS)

    Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I.

    2017-06-01

    The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

  12. Oxovanadium alkoxides: Structure, reactivity, and sup 51 V NMR characteristics. Crystal and molecular structures of VO(OCH sub 2 CH sub 2 Cl) sub 3 and VOCl sub 2 (THF) sub 2 H sub 2 O

    SciTech Connect

    Priebsch, W.; Rehder, D. )

    1990-08-08

    The vanadyl esters VO(OR){sub 3} (R = Me, Et, Pr, iPr, sBu, tBu, CH{sub 2}CH{sub 2}F, CH{sub 2}CH{sub 2}Cl, CH{sub 2}CCl{sub 3}) have been prepared and their association properties in pentane investigated by {sup 51}V NMR. Limiting (low concentration) {delta}({sup 51}V) values depend on the bulk of R (highest {sup 51}V shielding for tBu). Shielding decreases with increasing concentration (more pronounced for small R groups), owing to the formation of oligomers, probably connected by {mu}-OR groups. The X-ray diffraction study of VO(OCH{sub 2}CH{sub 2}Cl){sub 3} reveals dimer association of molecules belonging to adjacent unit cells via long V-OR bonds (226.1 (2) pm), and a trigonal-bipyramidal geometry for each monomeric unit. From the reaction between VOCl{sub 3} and diols (glycol, 1,3-propanediol, 1,2-, 2,3-, 1,3-, and 1,4-butanediol), complexes are obtained that contain the {l brace}VOCl(OR){sub 2}{r brace} and {l brace}VOCl{sub 2}OR{r brace} moieties and the alcohol coordinated in the monofunctional or bifunctional (chelating and bridging) mode. The {sup 51}V NMR spectrum of VOCl{sub 2}OCH(Me)CH(Me)OH exhibits resolved {sup 51}V-{sup 35,37}Cl coupling: J({sup 51}V-{sup 35}Cl) = 100 Hz; J({sup 51}V-{sup 37}Cl) = 83 Hz. V{sup V}OCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}OH) reacts with 1,4-butanediol to form V{sup IV}OCl{sub 2}(THF){sub 2}(OH{sub 2}). In the presence of COCL{sub 3}, THF undergoes ether splitting, chlorination, and coordination to vanadium to yield VOCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}CH{sub 2}Cl). 35 refs., 7 figs., 7 tabs.

  13. Enthalpy of hydrophobic hydration separately estimated for each -CH2-, -CF2-, and -OCH2CH2- unit component of amphiphiles and of related compounds.

    PubMed

    Seimiya, Tsutomu

    2003-10-15

    The enthalpy of hydrophobic hydration, DeltaH(HH), was separately estimated for each apolar segment of amphiphiles and of related compounds. The specimens analyzed in this study were the homologs and analogs of sodium alkyl sulfate, alkyltrimethylammonium bromide, ammonium perfluoroalkylcarboxylate, and polyethylene glycols. The DeltaH(HH) was calculated from the adiabatic compressibility beta of aqueous solution systematically measured for each homologs at varying concentrations and temperatures. Those data reported in the previous paper were utilized. The DeltaH(HH) estimated for each -CH(2)-, -CF(2)-, and -OCH(2)CH(2)- segments in both hydrophobic and hydrophilic parts of the amphiphiles was found to change depending on its locations in the molecule. The DeltaH(HH) for the first -CH(2)- unit which is adjacent to the head sulfate group of H(CH(2))(n)SO(4)Na was found to be negligibly small; however, it increases gradually as the position of the unit moves apart from the anionic head group and attains as large as -26.5 kcal/mol for the eighth -CH(2)-. The change of DeltaH(HH) of -CF(2)- unit in F(CF(2))(n)COONH(4) shows the similar tendency to H(CH(2))(n)SO(4)Na. The value of DeltaH(HH) is as small as -8 kcal/mol for the first -CF(2)-, however, it increases to -16 kcal/mol for the fifth -CF(2)-, which is 1.5 times larger than that of the fifth -CH(2)- of alkyl sulfate. Contrary to this, all the DeltaH(HH) of the methylenes of cationic surfactant ranging from the second to the eighth -CH(2)- units of H(CH(2))(n)N(CH(3))(3)Br take a similar value around -8 kcal/mol of -CH(2)- irrespective of their positions. The first -CH(2)- unit which is equivalent to that of quaternary ammonium [HCH(2)](4)NBr shows slightly higher value of -9.0 kcal/mol of the first -CH(2)- than those for the second to eighth -CH(2)-. This seems to suggest that the cationic core nitrogen has an enhancing effect on hydrophobic hydration. The hydration enthalpy DeltaH(OEH) of each oxyethylene (OE

  14. Correlation between stress-induced leakage current and dielectric degradation in ultra-porous SiOCH low-k materials

    SciTech Connect

    Wu, C. De Wolf, I.; Li, Y.; Leśniewska, A.; Varela Pedreira, O.; Marneffe, J.-F. de; Ciofi, I.; Verdonck, P.; Baklanov, M. R.; Bömmels, J.; Tőkei, Zs.; Croes, K.

    2015-10-28

    Stress-Induced Leakage Current (SILC) behavior during the dielectric degradation of ultra-porous SiOCH low-k materials was investigated. Under high voltage stress, SILC increases to a critical value before final hard breakdown. This SILC increase rate is mainly driven by the injected charges and is negligibly influenced by temperature and voltage. SILC is found to be transient and shows a t{sup −1} relaxation behavior, where t is the storage time at low voltages. This t{sup −1} transient behavior, described by the tunneling front model, is caused by both electron charging of neutral defects in the dielectric close to the cathode interface and discharging of donor defects close to the anode interface. These defects have a uniform density distribution within the probed depth range, which is confirmed by the observed flat band voltage shift results collected during the low voltage storage. By applying an additional discharging step after the low voltage storage, the trap energies and spatial distributions are derived. In a highly degraded low-k dielectric, the majority of defects have a trap depth between 3.4 eV and 3.6 eV and a density level of 1 × 10{sup 18 }eV{sup −1 }cm{sup −3}. The relation between the defect density N and the total amount of the injected charges Q is measured to be sub-linear, N ∼ Q{sup 0.45±0.07}. The physical nature of these stress-induced defects is suggested to be caused by the degradation of the Si-O based skeleton in the low-k dielectric.

  15. The Golgi α-1,6 mannosyltransferase KlOch1p of Kluyveromyces lactis is required for Ca2+/calmodulin-based signaling and for proper mitochondrial functionality

    PubMed Central

    2009-01-01

    Background Protein N-glycosylation is a relevant metabolic pathway in eukaryotes and plays key roles in cell processes. In yeasts, outer chain branching is initiated in the Golgi apparatus by the alpha-1,6-mannosyltransferase Och1p. Results Here we report that, in Kluyveromyces lactis, this glycosyltransferase is also required to maintain functional mitochondria and calcium homeostasis. Cells carrying a mutation in KlOCH1 gene showed altered mitochondrial morphology, increased accumulation of ROS and reduced expression of calcium signalling genes such as calmodulin and calcineurin. Intracellular calcium concentration was also reduced in the mutant cells with respect to the wild type counterparts. Phenotypes that occur in cells lacking the alpha-1,6-mannosyltransferase, including oxidative stress and impaired mitochondria functionality, were suppressed by increased dosage of KlCmd1p. This, in turn, acts through the action of calcineurin. Conclusions Proper functioning of the alpha-1,6-mannosyltransferase in the N-glycosylation pathway of K. lactis is required for maintaining normal calcium homeostasis; this is necessary for physiological mitochondria dynamics and functionality. PMID:20003441

  16. Fluid evolution in the H 2O-CH 4-CO 2-NaCl system during emerald mineralization at Gravelotte, Murchison Greenstone Belt, Northeast Transvaal, South Africa

    NASA Astrophysics Data System (ADS)

    Nwe, Yin Yin; Morteani, Giulio

    1993-01-01

    Fluid evolution during emerald mineralization at the Gravelotte emerald mine has been studied by microthermometry and laser Raman microprobe spectrometry. The emeralds and associated phenakites occur on the flanks of a highly metasomatised albitite pegmatoid body and in the biotite schists at and near its contact. The fluids lie in the H 2O-CH 4-CO 2-NaCl system and four types of inclusions are characterised based on time of trapping and fluid contents. The earliest type 1 inclusions, found in phenakites and the emeralds which formed from them, are low salinity (<6 wt% NaCl) with up to 18 mol% CH 4. The carbonic phase contains over 93 mol% CH 4 and variable small amounts of CO 2, C 2H 6, N 2, and H 2S. The solvus crest for this system lies at ≈400°C, closer to the H 2O end of the join. With time the fluids become less CH 4 rich and more saline. The type 2 fluids are highly variable in both CH 4-CO 2 contents and salinity, reflecting mixing of type 1 fluids with higher salinity brines. The late type 3 and 4 inclusions are CH 4-CO 2-free high salinity inclusions with up to 38 wt% NaCl. Trapping conditions for the type 1 fluids were around 450-500°C and 4 kb based on model isochores and geologic evidence. During the trapping of type 2 inclusions, fluid pressures probably fluctuated due to opening and resealing of fractures. Approximate P- T ranges of trapping for these and other later inclusions have been defined, minimum trapping temperatures for types 2, 3, and 4 being, respectively, 250, 150, and 240°C, and pressures in the range of 1-4 kb. Calculations of ƒ O 2 show an initial low ƒ O 2 between QFM and the synthetic graphite-CH 4 buffer for the type 1 fluids. This rises to above QFM in the later stages. Such low initial values are uncharacteristic of granitic pegmatite systems, and it is suggested that the phenakites formed in the post-magmatic stage of alkali metasomatism when the albitization took place. In the later stages, phenakite was converted to

  17. Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

    PubMed

    Yang, Jingying; Xie, Zuowei

    2015-04-14

    Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

  18. Transfer of Amide and 2-Methoxyethoxy Groups and Sodium Encapsulation in the Reaction of TaCl3[N(TMS)2]2 with Sodium Bis(2-methoxyethoxy)aluminum Hydride: X-ray Structure of [NaAl{N(TMS)2}(OCH2CH2OMe)3]2

    SciTech Connect

    Huang, Shih-Huang Huang; Wang, Xiaoping; Richmond, Michael G.

    2009-01-01

    The reaction between the tantalum compound TaCl3[N(TMS)2]2 and the hydridic reducing agent sodium bis(2-methoxyethoxy)aluminum hydride (Vitride) has been investigated in toluene solution at room temperature and found to afford the dimeric aluminate complex [NaAl{N(TMS)2}(OCH2CH2OMe)3]2 as the sole isolable product. The molecular structure of the product establishes the existence of a four-coordinate aluminum atom and the formal transfer of the 2-methoxyethoxy and bis(trimethylsilyl)amide groups to the aluminate product. The aggregation of two NaAl{N(TMS)2}(OCH2CH2OMe)3 units serves to bind the two sodium cations in a crown-ether fashion through six ancillary oxygen atoms.

  19. VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITIES, AND CRITICAL PROPERTIES OF SOME FLUORINATED ETHERS: CF3OCF2OCF3, CF3OCF2 CF2H, c-CF2CF2CF2O, CF3OCF2H, AND CF3OCH3; AND OF CCl3F AND CF2ClH

    EPA Science Inventory

    Vapor pressures, compressibilities, expansivities, and molar volumes of the liquid phase have been measured between room temperature and the critical temperature for a series of fluorinated ethers: CF3OCF2OCF3, CF3OCF2CF2H, c-CF2CF2CF2O, CF3OCF2H, and CF3OCH3. Vapor-phase non-ide...

  20. VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITIES, AND CRITICAL PROPERTIES OF SOME FLUORINATED ETHERS: CF3OCF2OCF3, CF3OCF2 CF2H, c-CF2CF2CF2O, CF3OCF2H, AND CF3OCH3; AND OF CCl3F AND CF2ClH

    EPA Science Inventory

    Vapor pressures, compressibilities, expansivities, and molar volumes of the liquid phase have been measured between room temperature and the critical temperature for a series of fluorinated ethers: CF3OCF2OCF3, CF3OCF2CF2H, c-CF2CF2CF2O, CF3OCF2H, and CF3OCH3. Vapor-phase non-ide...

  1. Synthesis and characterization of a new monophosphate (5-Cl-2,4-(OCH{sub 3}){sub 2}C{sub 6}H{sub 2}NH{sub 3})H{sub 2}PO{sub 4}

    SciTech Connect

    Kefi, R.; Abid, S.; Nasr, C. Ben . E-mail: cherif.bennasr@fsb.rnu.tn; Rzaigui, M.

    2007-03-22

    Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation 5-chloro(2,4-dimethoxy)anilinium monophosphate H{sub 2}PO{sub 4} are given. This new compound crystallizes in the monoclinic system, with the space group P2{sub 1}/c and the following parameters: a=5.524(2)A, b=9.303(2)A, c=23.388(2)A, {beta}=90.66(4), V=1201.8(2)A{sup 3}, Z=4 and D{sub x}=1.573gcm{sup -3}. Crystal structure has been determined and refined to R=0.031 and R{sub w}=0.080 using 1702 independent reflections. Structure can be described as an infinite (H{sub 2}PO{sub 4}){sub n}{sup n-} corrugated chains in the a-direction. The organic groups (5-Cl-2,4-(OCH{sub 3}){sub 2}C{sub 6}H{sub 2}NH{sub 3}){sup +} are anchored between adjacent polyanions through multiple hydrogen bonds. This compound is also investigated by IR, thermal, and solid-state, {sup 13}C, {sup 31}P MAS NMR spectroscopies.

  2. Photochemical properties of hydrofluoroethers CH3OCHF2, CH3OCF3, and CHF2OCH2CF3: reactivity toward OH, IR absorption cross sections, atmospheric lifetimes, and global warming potentials.

    PubMed

    Orkin, Vladimir L; Khamaganov, Victor G; Guschin, Andrey G

    2014-11-13

    Rate constants for the gas phase reactions of OH radicals with three partially fluorinated ethers, CH3OCF3 (kHFE-143a), CH3OCHF2 (kHFE-152a), and CHF2OCH2CF3 (kHFE-245fa2), were measured using a discharge flow-electron paramagnetic resonance technique over the temperature range 298-460 K. The temperature dependences of the rate constants can be represented by the following expressions: kHFE-143a(T) = (1.10 ± 0.20) × 10(-12) × exp{-(1324 ± 61)/T} cm(3) molecule(-1) s(-1); kHFE-152a(T) = (11.6 ± 4.2) × 10(-12) × exp{-(1728 ± 133)/T} cm(3) molecule(-1) s(-1); and kHFE-245fa2(T) = (3.04 ± 0.57) × 10(-12) × exp{-(1665 ± 66)/T} cm(3) molecule(-1) s(-1). The atmospheric lifetimes due to reactions with tropospheric OH were estimated to be 5.2, 1.9, and 5.6 years, respectively. The IR absorption cross sections of these fluorinated ethers were measured between 400 and 2000 cm(-1), and their global warming potentials were estimated.

  3. [Ni(OH)3W6O18(OCH2)3CCH2OH]4–: the first tris-functionalized Anderson-type heteropolytungstate† †Electronic supplementary information (ESI) available: Experimental procedures, synthesis details, characterization data, including IR, ESI-MS, TGA, elemental analysis and X-ray crystallography with CIF file. CCDC 1477611. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6cc04326g Click here for additional data file. Click here for additional data file.

    PubMed Central

    Gumerova, Nadiia I.; Roller, Alexander

    2016-01-01

    Na2[TMA]2[Ni(OH)3W6O18(OCH2)3CCH2OH]·9H2O represents the first covalent tris-functionalized Anderson-type heteropolytungstate and was characterized by single-crystal X-ray diffraction, electrospray ionization mass spectrometry, TGA and IR spectroscopy. Zeta potential measurements in solutions containing human serum albumin were performed to investigate electrostatic interactions with [Ni(OH)3W6O18(OCH2)3CCH2OH]4–. PMID:27355393

  4. Structure of the puf operon of the obligately aerobic, bacteriochlorophyll alpha-containing bacterium Roseobacter denitrificans OCh114 and its expression in a Rhodobacter capsulatus puf puc deletion mutant.

    PubMed Central

    Kortlüke, C; Breese, K; Gad'on, N; Labahn, A; Drews, G

    1997-01-01

    Roseobacter denitrificans (Erythrobacter species strain OCh114) synthesizes bacteriochlorophyll a (BChl) and the photosynthetic apparatus only in the presence of oxygen and is unable to carry out primary photosynthetic reactions and to grow photosynthetically under anoxic conditions. The puf operon of R. denitrificans has the same five genes in the same order as in many photosynthetic bacteria, i.e., pufBALMC. PufC, the tetraheme subunit of the reaction center (RC), consists of 352 amino acids (Mr, 39,043); 20 and 34% of the total amino acids are identical to those of PufC of Chloroflexus aurantiacus and Rubrivivax gelatinosus, respectively. The N-terminal hydrophobic domain is probably responsible for anchoring the subunit in the membrane. Four heme-binding domains are homologous to those of PufC in several purple bacteria. Sequences similar to pufQ and pufX of Rhodobacter capsulatus were not detected on the chromosome of R. denitrificans. The puf operon of R. denitrificans was expressed in trans in Escherichia coli, and all gene products were synthesized. The Roseobacter puf operon was also expressed in R. capsulatus CK11, a puf puc double-deletion mutant. For the first time, an RC/light-harvesting complex I core complex was heterologously synthesized. The strongest expression of the R. denitrificans puf operon was observed under the control of the R. capsulatus puf promoter, in the presence of pufQ and pufX and in the absence of pufC. Charge recombination between the primary donor P+ and the primary ubiquinone Q(A)- was observed in the transconjugant, showing that the M and L subunits of the RC were correctly assembled. The transconjugants did not grow photosynthetically under anoxic conditions. PMID:9286973

  5. Ab Initio Variational Transition State Theory and Master Equation Study of the Reaction of (OH){sub 3}SiOCH{sub 2} + CH{sub 3} {<- ->} (OH){sub 3}SiOC{sub 2}H{sub 5}

    SciTech Connect

    Nurkowski, Daniel; Klippenstein, Stephen J.; Georgievskii, Yuri; Verdicchio, Marco; Jasper, Ahren W.; Akroyd, Jethro; Mosbach, Sebastian; Kraft, Markus

    2015-05-01

    In this paper we use variable reaction coordinate variational transition state theory (VRC-TST) to calculate the reaction rate constants for the two reactions, R1: (OH)(3)SiOCH2 + CH3 reversible arrow (OH)(3)SiOC2H5, and R2: CH2OH + CH3 reversible arrow C2H5OH. The first reaction is an important channel during the thermal decomposition of tetraethoxysilane (TEOS), and its rate coefficient is the main focus of this work. The second reaction is analogous to the first and is used as a basis for comparison. The interaction energies are obtained on-the-fly at the CASPT2(2e,2o)/cc-pVDZ level of theory. A one-dimensional correction to the sampled energies was introduced to account for the energetic effects of geometry relaxation along the reaction path. The computed, high-pressure rate coefficients were calculated to be, R1: k(1) = 2.406x10(-10)T(-0.301) exp(-271.4/T) cm(3) molecule(-1) s(-1) and R2: k(2) = 1.316x10(-10)T(-0.189) exp(-256.5/T) cm(3) molecule(-1) s(-1). These rates differ fromeach other by only 10%-30% over the temperature range 300-2000 K. A comparison of the computed rates with experimental data shows good agreement and an improvement over previous results. The pressure dependency of the reaction R1 is explored by solving a master equation using helium as a bath gas. The results obtained show that the reaction is only weakly pressure dependent over the temperature range 300-1700 K, with the predicted rate constant being within 50% of its high-pressure limit at atmospheric pressure.

  6. Structural consequences of the one-electron reduction of d4 [Mo(CO)2(eta-PhC[triple bond]CPh)Tp']+ and the electronic structure of the d5 radicals [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {L = CO and P(OCH2)3CEt}.

    PubMed

    Adams, Christopher J; Bartlett, Ian M; Boonyuen, Supakorn; Connelly, Neil G; Harding, David J; Hayward, Owen D; McInnes, Eric J L; Orpen, A Guy; Quayle, Michael J; Rieger, Philip H

    2006-07-28

    Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis.

  7. {sup 203,205}Tl NMR Studies of Crystallographically Characterized Thallium Alkoxides. X-Ray Structures of [Tl(OCH{sub 2}CH{sub 3})]4 and [Tl(OAr)]{sub infinity} where OAr = OC{sub 6}H{sub 3}(Me){sub 2}-2,6 and OC{sub 6}H{sub 3}(Pr{sup i}){sub 2}-2,6

    SciTech Connect

    ZECHMANN,CECILIA A.; BOYLE,TIMOTHY J.; PEDROTTY,DAWN M.; ALAM,TODD M.; LANG,DAVID P.; SCOTT,BRIAN L.

    2000-07-25

    [Tl(OCH{sub 2}CH{sub 3})]{sub 4}, (1) was reacted with excess HOR to prepare a series of [Tl(OR)]{sub n} where OR= OCHMe{sub 2} (2, n = 4), OCMe{sub 3} (3, n = 4), OCH{sub 2}CMe{sub 3} (4, n = 4), OC{sub 6}H{sub 3}(Me){sub 2}-2,6 (5, n = {infinity}), and OC{sub 6}H{sub 3}(Pr{sup i}){sub 2}-2,6 (6, n = {infinity}). Single crystal X-ray diffraction was used to determine the structure of compounds ligated by more sterically demanding ligands. Compound 4 was found to adopt a cubane structure, while 5 and 6 formed linear polymeric structures. These compounds were additionally characterized by {sup 203,205}Tl solution and {sup 205}Tl solid state NMR. Compounds 1--4 were found to remain intact in solution while the polymeric species, 5 and 6, appeared to be fluxional. While variations in the solution and solid state structures for the tetrameric [Tl(OR)]{sub 4} and polymeric [Tl(OAr)]{sub {infinity}} may be influenced by the steric hindrance of their respective ligands, the covalency of the species is believed to be more an effect of the parent alcohol acidity.

  8. Vanadium complexes of the N(CH2CH2S)3(3-) and O(CH2CH2S)2(2-) ligands with coligands relevant to nitrogen fixation processes.

    PubMed

    Davies, S C; Hughes, D L; Janas, Z; Jerzykiewicz, L B; Richards, R L; Sanders, J R; Silverston, J E; Sobota, P

    hydrolysis and to [V(NS3)(NCPh3)] (11) by reaction with ClCPh3. Compound 10 is converted into 1 by [NMe4]OH and to [V(NS3)NLi(THF)2] (12) by LiNPri in THF. A further range of imido complexes [V(NS3)(NR4)] (R4 = C6H4Y-4 where Y = H (13a), OMe (13b), Me (13c), Cl (13d), Br (13e), NO2 (13f); R4 = C6H4Y-3, where Y = OMe (13g); Cl (13h); R4 = C6H3Y2-3,4, where Y = Me (13i); Cl (13j); R4 = C6H11 (13k)) has been prepared by reaction of 1 with R4NCO. The precursor complex [V(OS2)O(dipp)] (14) [OS2(2-) = O(CH2CH2S)2(2-)] has been prepared from [VO(OPri)3], Hdipp, and OS2H2. It reacts with NH2NMe2 to give [V(OS2)(NNMe2)(dipp)] (15) and with N3SiMe3 to give [V(OS2)(NSiMe3)(dipp)] (16). A second oxide precursor, formulated as [V(OS2)1.5O] (17), has also been obtained, and it reacts with SiMe3NHNMe2 to give [V(OS2)(NNMe2)(OSiMe3)] (18). The X-ray crystal structures of the complexes 2b, 2c, 4, 6, 7a, 8a, 9, 10, 13d, 14, 15, 16, and 18 have been determined, and the 51V NMR and other spectroscopic parameters of the complexes are discussed in terms of electronic effects.

  9. Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H & fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2)

    NASA Astrophysics Data System (ADS)

    Bai, Feng-Yang; Ma, Yuan; Lv, Shuang; Pan, Xiu-Mei; Jia, Xiu-Juan

    2017-01-01

    In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2 and CF3OCF2CF2• in the presence of O2 and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2 and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230–350 K are: k T(1) = 5.00 × 10‑24T3.57 exp(‑849.73/T), k T(2) = 1.79 × 10‑24T4.84 exp(‑4262.65/T), kT(3) = 1.94 × 10‑24 T4.18 exp(‑884.26/T), and k T(4) = 9.44 × 10‑28T5.25 exp(‑913.45/T) cm3 molecule‑1 s‑1.

  10. Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H & fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2)

    PubMed Central

    Bai, Feng-Yang; Ma, Yuan; Lv, Shuang; Pan, Xiu-Mei; Jia, Xiu-Juan

    2017-01-01

    In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2 and CF3OCF2CF2• in the presence of O2 and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2 and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230–350 K are: k T(1) = 5.00 × 10−24T3.57 exp(−849.73/T), k T(2) = 1.79 × 10−24T4.84 exp(−4262.65/T), kT(3) = 1.94 × 10−24 T4.18 exp(−884.26/T), and k T(4) = 9.44 × 10−28T5.25 exp(−913.45/T) cm3 molecule−1 s−1. PMID:28067283

  11. An ab initio study on tunability of σ-hole interactions in XHS:PH2Y and XH2P:SHY complexes (X = F, Cl, Br; Y = H, OH, OCH3, CH3, C2H5, and NH2).

    PubMed

    Esrafili, Mehdi D; Mohammadirad, Nafiseh

    2015-07-01

    Quantum chemical calculations are performed to investigate the tunability of σ-hole interactions in chalcogen-bonded XHS:PH2Y and pnicogen-bonded XH2P:SHY complexes, where X  =  F, Cl, Br and Y  =  H, OH, OCH3, CH3, C2H5, NH2. The formation of these binary complexes can be understood in terms of molecular electrostatic potentials (MEPs), considering the P and S atoms as an electron acceptor or an electron donor in the chalcogen and pnicogen bonds. The strength of the XHS:PH2Y and XH2P:SHY complexes for a given Y increases as follows: X = Br < Cl < F. In addition, an acceptable linear relationship is found between the interaction energies and the magnitudes of the product of most positive and negative MEPs. This finding along with the electron density difference maps provides a clear picture of the electrostatic nature of the interactions in the XHS:PH2Y and XH2P:SHY complexes. The calculated spin-spin coupling constants across the chalcogen bond interactions in the XHS:PH2Y complexes display a quadratic dependence with the P···S binding distance.

  12. Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

    PubMed

    Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena

    2008-10-01

    The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors

  13. Reactivity of [{l{underscore}brace}Mn{sup 4}(salpn){r{underscore}brace}{sub 2}({micro}-O,{micro}-OCH{sub 3})]{sup +} and [{l{underscore}brace}Mn{sup IV}(salpn){r{underscore}brace}{sub 2}({micro}-O,{micro}-OH)]{sup +}: Effects of proton liability and hydrogen bonding

    SciTech Connect

    Baldwin, M.J.; Law, N.A.; Stemmler, T.L.; Kampf, J.W.; Penner-Hahn, J.E.; Pecoraro, V.L.

    1999-10-18

    It was previously shown that the addition of 1 equiv of a strong acid to [Mn{sup IV}(salpn)({micro}-O)]{sub 2}, 1, generates the oxo/hydroxo complex [{l{underscore}brace}Mn{sup IV}(salpn){r{underscore}brace}{sub 2}({micro}-O,{micro}-OH)](CF{sub 3}SO{sub 3}), 2, which emphasized the basicity of the {micro}{sub 2}-O{sup 2{minus}} units in the [Mn{sup IV}({micro}-O)]{sub 2} dimers. The authors now demonstrate the inherent nucleophilicity of those {micro}{sub 2}-O{sup 2{minus}} units by showing that the addition of methyl triflate to 1 results in formation of the oxo/methoxo-bridged Mn{sup IV} dimer [{l{underscore}brace}Mn{sup IV}(salph){r{underscore}brace}{sub 2}({micro}-O,{micro}-OCH{sub 3})](CF{sub 3}SO{sub 3}), 3. EXAFS analysis of 3 demonstrates that alkylation of an oxo bridge results in the same structural modification of the [Mn{sup IV}({micro}-O)]{sub 2} core as an oxo bridge protonation. Electrochemical and spectroscopic comparisons of 3 to 2 indicate that 3 is a good electronic structure analogue for 2 without the complication of proton lability and hydrogen bonding. Indeed, 2 and 3 react nearly identically with hydrogen peroxide and with strong acids. In contrast, the products of their reactions with amines, acetate, and triphenylphosphine are dramatically different. The proton lability of 2 results in simple proton transfer, circumventing the slower redox reactions of these substrates with 3. Isotopic labeling, kinetic, and EPR-monitored radical trap studies lead to a proposed reduction-oxidation mechanistic scheme for the reactions of 3 with amines and triphenylphosphine. The Mn{sup III} product of this reaction, [Mn{sup III}(salpn)(Ph{sub 3}PO)](CF{sub 3}SO{sub 3}), was isolated and crystallographically characterized as a dimerized complex. The redox nature of the reactions is confirmed by trapping of a reduced Mn intermediate which is identified by EPR spectroscopy. Comparison of the reactions of 2 and 3 demonstrates the dramatic effect of proton

  14. Energetics of the O-H bond and of intramolecular hydrogen bonding in HOC6H4C(O)Y (Y = H, CH3, CH2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds.

    PubMed

    Bernardes, Carlos E S; Minas da Piedade, Manuel E

    2008-10-09

    The energetics of the phenolic O-H bond in a series of 2- and 4-HOC 6H 4C(O)Y (Y = H, CH3, CH 2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH 3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds and of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y, was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-hydroxybenzaldehyde (2HBA), 4-hydroxybenzaldehyde (4HBA), 2'-hydroxyacetophenone (2HAP), 2-hydroxybenzamide (2HBM), and 4-hydroxybenzamide (4HBM), at 298.15 K, were determined by micro- or macrocombustion calorimetry. The corresponding enthalpies of vaporization or sublimation were also measured by Calvet drop-calorimetry and Knudsen effusion measurements. The combination of the obtained experimental data led to Delta f H m (o)(2HBA, g) = -238.3 +/- 2.5 kJ.mol (-1), DeltafHm(o)(4HBA, g) = -220.3 +/- 2.0 kJ.mol(-1), Delta f H m (o)(2HAP, g) = -291.8 +/- 2.1 kJ.mol(-1), DeltafHm(o)(2HBM, g) = -304.8 +/- 1.5 kJ.mol (-1), and DeltafHm(o) (4HBM, g) = -278.4 +/- 2.4 kJ.mol (-1). These values, were used to assess the predictions of the B3LYP/6-31G(d,p), B3LYP/6-311+G(d,p), B3LYP/aug-cc-pVDZ, B3P86/6-31G(d,p), B3P86/6-311+G(d,p), B3P86/aug-cc-pVDZ, and CBS-QB3 methods, for the enthalpies of a series of isodesmic gas phase reactions. In general, the CBS-QB3 method was able to reproduce the experimental enthalpies of reaction within their uncertainties. The B3LYP/6-311+G(d,p) method, with a slightly poorer accuracy than the CBS-QB3 approach, achieved the best performance of the tested DFT models. It was further used to analyze the trends of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y evaluated by the ortho-para method and to compare the energetics of the phenolic O-H bond in 2- and 4-HOC 6H 4C(O)Y compounds. It was concluded that the O-H bond "strength" is systematically larger for 2-hydroxybenzoyl than for the corresponding 4-hydroxybenzoyl isomers mainly due to the presence of

  15. Smabarnens Kultur-Och Mediebarometer. (Barometer of Children's Cultural Activity).

    ERIC Educational Resources Information Center

    Filipson, Leni; Schyller, Ingela

    This is the first of a planned series of investigations of the media habits and other cultural activities of 3- to 8-year-old Swedish children. Diagrams show the percent of children who use the various media on an average day and the frequency of their participation in such activities as visits to the theater, museum, or library. The amount of…

  16. Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH}

    NASA Astrophysics Data System (ADS)

    Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.

    2013-09-01

    Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

  17. Kop- och saljsystem inom barnomsorgen: Konsekvenser for Personal, Foraldrar och barn (A New Charging System in Child Care: Consequences for Personnel, Parents, and Children).

    ERIC Educational Resources Information Center

    Ekholm, Bodil; Ellstrom, Eva

    The aim of this study was to examined the impact of a new charging system in child care in two different Swedish municipalities, on personnel, parents, and children. Four day care centers situated in different socioeconomic areas were studied. A qualitative approach was used, and data were collected by means of interviews and a questionnaire.…

  18. Dagliga Separationer och Tidig Daghemsstart (Daily Separations and Early Entry into Day Care).

    ERIC Educational Resources Information Center

    Harsman, Ingrid

    The purpose of this thesis [Swedish language with English abstract and summary] was to study the reactions of infants when they started attending day care centers and to elucidate the process of adjustment. The theoretical perspective employed is the J. Bowlby/M. Ainsworth attachment theory. U. Bronfenbrenner's ecological theory of human…

  19. Aetervinning av faerg och ridaevatten med ultrafiltrering (recycling of paint and water curtains with ultrafiltration)

    SciTech Connect

    Fortkamp, U.; Allard, A.S.; Ekengren, O.

    1997-12-01

    Painting in spray booths causes overspray that is collected by a water curtain. The mixture of water and paint is commonly treated by means of precipitation. By means of this method, water can be used again but a paint sludge is created. Within this project, it was investigated how the paint as well as the water can be recycled. Separation by membrane filtration was tested for different paints in laboratory scale (0.2 liter volume). It was possible to separate all tested paints from the water and to concentrate it. At large scale (15 to 75 liters volume), an emulsion paint and a dispersion paint were tested. Under the tested conditions, it was slightly easier to concentrate the emulsion paint than the dispersion paint. It was possible to concentrate the paints to the original dry substance percentage. An important aspect of membrane filtration is cleaning of the membrane when the performance decreases. It was possible to clean all the tested membranes, but in many cases it was difficult. A ceramic membrane and a membrane of polyaramide showed the best results with regard to flux and cleaning of the membrane under the tested conditions. During the performance of the project two new applications of membrane filtration of paint were found. The method can be used for waste minimization by only separating the paint in an easy way at low costs. A third application is treating cleaning water from paint manufacturing.

  20. Daghemsvistelse I Retrospektivt Perspektiv: En teori- och metodprovande studie (Daycare in Retrospect).

    ERIC Educational Resources Information Center

    Torstenson-Ed, Tullie

    This Swedish language report describes a preliminary study to test a retrospective life-history-inspired approach to studying children's experiences in a day care center, and whether children's experiences vary in different educational contexts and in relation to the teachers' experiences. The theoretical part of the study dealt with theories of…

  1. An Analysis of Textual Cohesion in a Passage from Maria Gripe's "Hugo och Josefin."

    ERIC Educational Resources Information Center

    Andersson, Erik

    Sentence-by-sentence analysis of factual or propositional cohesion in the first 29 lines of a Swedish children's story finds several sources of coherence that contribute to its cohesion. First, the text receives much coherence from its description of a single event, a situation where happenings are normal and expected. Second, a rather primitive…

  2. Dagliga Separationer och Tidig Daghemsstart (Daily Separations and Early Entry into Day Care).

    ERIC Educational Resources Information Center

    Harsman, Ingrid

    The purpose of this thesis [Swedish language with English abstract and summary] was to study the reactions of infants when they started attending day care centers and to elucidate the process of adjustment. The theoretical perspective employed is the J. Bowlby/M. Ainsworth attachment theory. U. Bronfenbrenner's ecological theory of human…

  3. Library Work and Automation; A Summary of the Swedish Report "Biblioteksarbete och Automatisk Databehandling."

    ERIC Educational Resources Information Center

    Royal Library, Stockholm (Sweden).

    The work of the Committee on the use of automation in Swedish research libraries has differed from that of a normal study group by virtue of its heavy concentration on the practical aspects of library catalog work, the present status of which is the main theme of this report. The model presented implies total and simultaneous integration of all…

  4. Experimental and DFT study of nitrogen atoms interactions with SiOCH low- κ films

    NASA Astrophysics Data System (ADS)

    Voronina, Ekaterina N.; Mankelevich, Yuri A.; Rakhimova, Tatyana V.; Palov, Alexander P.; Lopaev, Dmitry V.; Zyryanov, Sergey M.; Zotovich, Alexey I.; Baklanov, Mikhail R.

    2017-05-01

    Damage of porous organosilicate glass (OSG) films with low dielectric constants (low-κ films) in plasma processing is a critical problem for modern microelectronics. For this problem, understanding and revealing of basic reaction steps for radicals etching and damage are of importance. Previously we have studied experimentally and theoretically the etching and damage of low-κ dielectric films under oxygen and fluorine atoms. Here the effects of N atoms on OSG films are studied experimentally by Fourier Transform InfraRed (FTIR) spectroscopy method and theoretically by density functional theory (DFT) method. Experimental FTIR spectra are compared with calculated vibrational spectra to reveal the relevant surface SiCHxNy groups which could be produced in multi-step reactive collisions of N atoms in ground and lower metastable states with OSG low-κ dielectric films. Contribution to the Topical Issue "Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces", edited by A.N. Grum-Grzhimailo, E.V. Gryzlova, Yu V. Popov, and A.V. Solov'yov.

  5. Stereodynamics study of the exchange reaction O (3P) + CH4 → H + OCH3

    NASA Astrophysics Data System (ADS)

    Cheng, Da-Hai; Yuan, Jiu-Chuang; Yang, Tian-Gang; Chen, Mao-Du

    2013-06-01

    A new London—Eyring—Polanyi—Sato potential energy surface is employed in this work to study the stereo properties of the O(3P) + CH4 → H + CH3O reaction in its rovibrationally ground state using the quasiclassical trajectory method (QCT). Our calculations are performed at a range of collision energies, Ec = 1.5 eV~ 3.5 eV, and the excitation function obtained by the QCT method accords well with the experimental data. The product rotational polarization is calculated, and the product shows a strong rotational polarization in the centre-of-mass coordinate system. The orientation of the product rotational angular momenta is sensitive to the increase in collision energy, and the alignment of the product rotational angular momenta shows some of the properties of the heavy heavy—light mass combination reactions. In the isotopic substituted reaction study, when the H atoms in methane are replaced by D atoms, the rotational polarization is obviously reduced. The polarization-dependent differential cross section is also studied by this QCT calculation to provide detailed information about the rotational alignment and orientation of the product.

  6. Characterization of Air Particles Giving False Responses with Biological Detectors

    DTIC Science & Technology

    1975-07-01

    cbserve the alpha group representing biologicals, natural and man-made foers and hairs, fertilizers and food products gave particles in which 67% showed...epithelial cells + 4- -+ 4- + + flyash + + + + fungus +. + 4 4.- glass particles + 4- + hematite D + + metal, white - ? paint spray or chips 1 . 4- . paper

  7. a Comparison of the Molecular Structures of C_4H_9OCH_3, C_4H_9SCH_3, C_5H_{11}OCH_3, and C_5H_{11}SCH_3 Using Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Long, Brittany E.; Betancur, Juan; Choi, Yoon Jeong; Cooke, S. A.; Grubbs, G. S., II; Ogulnick, Jonathan; Holmes, Tara

    2017-06-01

    Pure rotational spectra of the title molecules have been recorded using chirped pulse Fourier transform microwave spectroscopy. Under our experimental conditions only one conformer has been observed for each of the four compounds. These conformers have torsional angles of CXCC = 180^o, XCCC = 60^o, CCCC = 180^o, and, for the C_5H_{11}-X-CH_3 species, CCCC_{Methyl} = 180^o. These angles correspond to anti-gauche-anti conformations for the butyl methyl ether/thioether species, and anti-gauche-anti-anti conformations for the pentyl methyl ether/thioether species. Splittings due to the internal rotation of the X-CH_3 group are observed in both butyl species but are not observed in the pentyl species. The barrier to the X-CH_3 internal rotation has been investigated through spectral analyses and quantum chemical calculations. The differences in the internal rotation barrier between the ethers and thioethers will be discussed and will further be compared to the barriers obtained for similar molecules.

  8. Characterization by NMR of reactants and products of hydrofluoroether isomers, CF3(CF2)3OCH3 and (CF3)2C(F)CF2OCH3, reacting with isopropyl alcohol.

    PubMed

    Knachel, Howard C; Benin, Vladimir; Moddeman, William E; Birkbeck, Janine C; Kestner, Thomas A; Young, Tanya L

    2013-07-01

    The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the (1)H and (19)F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine and hydrogen atoms on the hydrofluoroethers and isopropyl alcohol are traced through the reactions to their values in the products--esters, isopropylmethyl ether, and HF. These spectral positions, multiplicities, and coupling constants are presented in table format and as figures to clarify the transformations observed as the samples age. Copyright © 2013 John Wiley & Sons, Ltd.

  9. Sma Barn Pa Daghem: En studie av personalens samspel med barn och foraldrar vid lamning, hamtning och fri lek (Infants at Day Care: A Study of Staff Interaction with Children and Their Parents during Leaving, Collecting and Free Play).

    ERIC Educational Resources Information Center

    Lothigius, Anita Holmstedt

    This thesis presents a picture of how staff interact with infants (age group 1-3 years old) and parents at three day care centers. The study focused on the situations of leaving and collecting the children and the children's time of free play both in and outdoors. The theoretical content has an attachment/psycho-dynamical perspective with emphasis…

  10. Daghemsklimat: Bakgrund, syfte och matinstrument. (The Climate of Day-Care Centers: Theoretical Backgrounds and Methods of Measurement).

    ERIC Educational Resources Information Center

    Ekholm, Bodil; And Others

    Using a new approach to studying day care centers, this study focused on the total climate of the day care center and the climate's effects on children's social and emotional behavior. A theoretical model for analyzing day care climate is presented. The model includes variables such as job satisfaction, work atmosphere, interactions between…

  11. Speciallararens Kunskaper Och Kompetens: Intervjuer med tio speciallarare (The Special Teacher's Knowledge and Competence: Interviews with Ten Special Teachers).

    ERIC Educational Resources Information Center

    Vernersson, Inga-Lill

    This thesis reports on a study in which 10 Swedish special education teachers were interviewed concerning the following six topics: (1) personal background and choice of a career; (2) professional knowledge; (3) the role of a special education teacher; (4) educational goals and methods; (5) cooperation; and (6) thoughts about the future.…

  12. Applying Commercial Style Acquisition Practices to the Procurement of Commercially Available Aircraft

    DTIC Science & Technology

    1992-09-01

    95 v List of Tables Table Page 1. U S Commercial Transport Industry...how tunig knh me*_ __ Nov" s Oodmits ftn ama ftomen"-MunS onw at mew goi ftob vows foer 1 0 ea gait os ood man Im U *Askwye emu" bun addon0 amgood sammtow...AD-A258 143 AFIT/GCM/VLSYI92-6 DTIC S LECTES EC 1792D CA719 APPLYING COMMIERCIAL STYLE ACQUISITION PRACTICES TO THE PROCUREMENT OF COMMIERCIALLY

  13. Inventory Manager’s Workstation for the Aviation Supply Office

    DTIC Science & Technology

    1988-12-01

    PHANTOM USER LOGIN MACRO ............... 148 APPENDIX H INVENTORY MANAGEMENT MACROS .............. 165 LIST OF REFERENCES...support the DSS software. Each of 42 MINE The Connectivity DcM ionnDecision Guide moreThenFile exchange foer spephera t no only? no Disk/cartrIdge yes...The Sun 3/160 executes a batch program that logs in a phantom user on the server. The phantom user enters ALIS. (2:30 am, nightly) * As the phantom

  14. An ab initio determination of the bending-torsion-torsion spectrum of dimethyl ether, CH3OCH3 and CD3OCD3

    NASA Astrophysics Data System (ADS)

    Senent, M. L.; Moule, D. C.; Smeyers, Y. G.

    1995-04-01

    We have calculated the potential energy hypersurface of dimethyl ether with respect to the COC bending coordinate α and the torsional angles of the two methyl groups, θ1 and θ2. Two sets of ab initio calculations were carried out. The first was made at the level MP2/6-31G(d,p) in which the structural coordinates were fully relaxed except for the grid points on the hypersurface. More extensive calculation were carried out with MP4 corrections for electron correlation with the same molecular structure. The torsional bending Hamiltonian matrix was symmetrized by the operations of the G36 nonrigid group and was solved variationally. The effect of explicitly considering the bending mode in the three-dimensional treatment was determined by a comparison to the two-dimensional model in which the flexibility of the frame was absorbed into the calculation by the fully relaxed method. It was found that the three-dimensional calculation gave a much better account of the sin(3θ1)sin(θ2) intermode coupling than the two-dimensional treatment.

  15. Att Tolka Barns Signaler: Gravt utvecklingsstorda flerhandikappade barns lek och kommunikation (To Interpret Childrens' Signals: Play and Communication in Profoundly Mentally Retarded and Multiply Handicapped Children).

    ERIC Educational Resources Information Center

    Brodin, Jane

    Written in Swedish with an English-language summary, this report describes a study which examined the interaction between mothers or caregivers and their children with profound mental retardation and multiple disabilities, particularly looking at the function of play in communicative interaction. The six children all had five or six handicaps in…

  16. Proposal of New Precursors for Plasma-Enhanced Chemical Vapor Deposition of SiOCH Low-k Films with Plasma Damage Resistance

    NASA Astrophysics Data System (ADS)

    Yoshi Ohashi,; Nobuo Tajima,; Yonghua Xu,; Takeshi Kada,; Shuji Nagano,; Hideharu Shimizu,; Satoshi Hasaka,

    2010-05-01

    We propose new precursors for bulk low-k films with plasma damage resistance. Our newly designed precursors contain long-chain hydrocarbon groups such as i-butyl and n-propyl groups. Using these precursors, we successfully produced films containing Si-CH2-Si groups by plasma-enhanced chemical vapor deposition (PECVD). The plasma damage resistance of these films under NH3 plasma treatment was studied. It was found that the increase in the k-value (Δ k) is smaller in films with more Si-CH2-Si groups.

  17. Proposal of New Precursors for Plasma-Enhanced Chemical Vapor Deposition of SiOCH Low-k Films with Plasma Damage Resistance

    NASA Astrophysics Data System (ADS)

    Ohashi, Yoshi; Tajima, Nobuo; Xu, Yonghua; Kada, Takeshi; Nagano, Shuji; Shimizu, Hideharu; Hasaka, Satoshi

    2010-05-01

    We propose new precursors for bulk low-k films with plasma damage resistance. Our newly designed precursors contain long-chain hydrocarbon groups such as i-butyl and n-propyl groups. Using these precursors, we successfully produced films containing Si-CH2-Si groups by plasma-enhanced chemical vapor deposition (PECVD). The plasma damage resistance of these films under NH3 plasma treatment was studied. It was found that the increase in the k-value (Δk) is smaller in films with more Si-CH2-Si groups.

  18. Knowledge and Life-Experiences: Finland Seen through Its Libraries and Information Services = Kunskap och Upplevelser: Finland som BDI-land.

    ERIC Educational Resources Information Center

    Laaksovirta, Tuula H.; Haavisto, Tuula

    This illustrated publication, printed in both English and Finnish, describes Finland's libraries and information services. Topics covered include: (1) library users; (2) the conceptual role of the library; (3) the growth and development of the library system through Finland's agrarian, industrial, and budding infotech social phases; (4) the…

  19. Still Picture Telephones for Persons with Profound Mental Retardation. Telematik och Handikapp, Rapport 92:9 (Telematics and Disability, Report 92:9).

    ERIC Educational Resources Information Center

    Brodin, Jane; Bjorck-Akesson, Eva

    This project studied the use of still picture telephones by four Swedish adults (ages 25-45) with profound mental retardation and additional severe disabilities. After 5 to 6 months of subjects employing still picture telephones on a regular basis in their daily lives, relatives, staff from group homes, and other caregivers completed…

  20. 12 Daghem: Beskrivning av uppfostringsklimat och sociala relationer (Twelve Day Care Centers: A Multisite Comparison of Day-Care Climate and Social Relations).

    ERIC Educational Resources Information Center

    Ekholm, Bodil; Hedin, Anna

    Twelve day care centers in a Swedish commune were systematically observed. Centers were selected on the basis of responses to a questionnaire on attitudes about upbringing which was answered by all the personnel at the 104 day care centers in the commune. Four of the selected centers represented a so-called "present-focused" upbringing…

  1. Daghemsklimat: Uppfostringsattityder, engagemang och kanslor infor arbetet hos daghemspersonal. (Attitudes of Child-Rearing, Engagements and Feelings towards Work by Personnel at Day-Care Centers).

    ERIC Educational Resources Information Center

    Jonsson, Arne

    Approximately 900 employees in the day care centers in one Swedish commune answered a questionnaire measuring child rearing attitudes and personnel's engagement and feelings concerning their work with the children. The child rearing attitudes were described as either "present-focused" or "future-focused." Of particular interest…

  2. Principles of Biochemistry, Second Edition by H. Robert Horton, Laurence A. Moran, Raymond S. Ochs, J. David Rawn, K. Gray Scrimgeour

    NASA Astrophysics Data System (ADS)

    Voige, William H.

    1997-02-01

    Prentice Hall: Upper Saddle River, NJ, 1996. xxix + 801 pp. Figs. and tables. 22.4 x 28.4 cm. This book follows the format that has become standard for biochemistry texts. Sections begin with short declarative statements of principles that are explained concisely in the following paragraphs. The best chapters proceed in a straightforward and logical manner. The lipids chapter is exemplary. A discussion of molecular structure, beginning with fatty acids, is followed by membrane structure, transport, and signal transduction.

  3. Fortursbarn och "vanliga" barn pa tolv daghem: Jamforande observationer. (Mainstreamed Children and "Ordinary" Children in Twelve Day-Care Centers: An Observational Study).

    ERIC Educational Resources Information Center

    Ekholm, Bodil; Hedin, Anna

    Observations of one mainstreamed child and one "ordinary child" at each of 12 day care centers were compared. Five of the 12 mainstreamed children were mentally retarded, and seven had a slight developmental retardation mainly due to deprivation. Observations of 10-minute duration, totaling 4 hours and dispersed across 7 days, focused on…

  4. Daghemsklimat: Uppfostringsattityder, engagemang och kanslor infor arbetet hos daghemspersonal. (Attitudes of Child-Rearing, Engagements and Feelings towards Work by Personnel at Day-Care Centers).

    ERIC Educational Resources Information Center

    Jonsson, Arne

    Approximately 900 employees in the day care centers in one Swedish commune answered a questionnaire measuring child rearing attitudes and personnel's engagement and feelings concerning their work with the children. The child rearing attitudes were described as either "present-focused" or "future-focused." Of particular interest…

  5. Li[B(OCH2CF3)4]: synthesis, characterization and electrochemical application as a conducting salt for LiSB batteries.

    PubMed

    Rohde, Michael; Eiden, Philipp; Leppert, Verena; Schmidt, Michael; Garsuch, Arnd; Semrau, Guenter; Krossing, Ingo

    2015-02-23

    A new Li salt with views to success in electrolytes is synthesized in excellent yields from lithium borohydride with excess 2,2,2-trifluorethanol (HOTfe) in toluene and at least two equivalents of 1,2-dimethoxyethane (DME). The salt Li[B(OTfe)4 ] is obtained in multigram scale without impurities, as long as DME is present during the reaction. It is characterized by heteronuclear magnetic resonance and vibrational spectroscopy (IR and Raman), has high thermal stability (Tdecomposition >271 °C, DSC) and shows long-term stability in water. The concentration-dependent electrical conductivity of Li[B(OTfe)4 ] is measured in water, acetone, EC/DMC, EC/DMC/DME, ethyl acetate and THF at RT In DME (0.8 mol L(-1) ) it is 3.9 mS cm(-1) , which is satisfactory for the use in lithium-sulfur batteries (LiSB). Cyclic voltammetry confirms the electrochemical stability of Li[B(OTfe)4 ] in a potential range of 0 to 4.8 V vs. Li/Li(+) . The performance of Li[B(OTfe)4 ] as conducting salt in a 0.2 mol L(-1) solution in 1:1 wt % DME/DOL is investigated in LiSB test cells. After the 40th cycle, 86 % of the capacity remains, with a coulombic efficiency of around 97 % for each cycle. This indicates a considerable performance improvement for LiSB, if compared to the standard Li[NTf2 ]/DOL/DME electrolyte system.

  6. [A Pichia pastoris with alpha-1, 6-mannosyltransferases deletion and its use in expression of HSA/GM-CSF chimera].

    PubMed

    Wang, Yue; Gong, Xin; Chang, Shao-Hong; Liu, Bo; Song, Miao; Huang, Hai-Hua; Wu, Jun

    2007-09-01

    Yeast is a widely used host for recombinant protein expression. However, glycoproteins derived from yeast contain N-glycan of high mannose type and are usually hyperglycosylated. alpha-1,6-mannosyltransferases gene (och1) encodes the enzyme that initiates the first step of out-chain elongation of high mannose type N-glycan in yeast, which is different from that in human. So, a high efficient method to knockout target gene by two-step recombination was established and was used to delete och1. In the first recombinant, a plasmid with och1::ADE1 and ura3 gene was linearized in the downstream of och1 and inserted to the och1 site of P. pastoris genome, where the upstream and downstream of och1 were duplicated. In the second recombinant, the duplicated fragments of och1 were exchanged and the och1 deletion strains were selected on the plates containing 5-FOA, but no adenine. Then the och1 deletion strain was applied to express an human serum albumin (HSA) granulocyte-macrophage colony-stimulating factor (GM-CSF) chimera. Different with the hyperglycosylated HSA/GM-CSF chimera expressed in wild type P. pastoris, the chimera expressed in the och1 deletion strain, contained smaller N-glycan. The results suggested that the och1 mutant yeast may be more suitable for production of recombinant glycoproteins. And the och 1 deletion strain could be used for further re-engineering to produce complex human glycoproteins.

  7. Studenters fritids--och motionsvanor i Umea och Madison. Ett bidrag till forstaelsen av Pierre Bourdieus vetenskapliga metodologi. Akademiska avhanlingar, Pedagogiska institutionen Nr. 58 (Leisure and Exercise Habits among Students in Umea and Madison. A Contribution to the Understanding of Pierre Bourdieu's Scientific Methodology. Academic Dissertation, Faculty of Social Sciences No. 58).

    ERIC Educational Resources Information Center

    Lofgren, Kent

    This study, presented in Swedish with an English summary, analyzed differences between student groups at Umea University, Sweden, and the University of Wisconsin-Madison in terms of study situations, experiences of the university environment, exercise and sports activities, and the connections between study and leisure time activities. The study…

  8. Komvux-Proven i Engelska VT 1989: Jamforelser mellan Komvux och Gymnasieskolan i Fraga om Provresultat och Betyg. Rapport nr 1990:06. (National Standardized Tests in English in Adult Education 1989: Comparison between Adult and Upper Secondary Students Test Results and School Leaving Grades. Report No. 1990:06).

    ERIC Educational Resources Information Center

    Oscarson, Mats

    This report describes the results of adult education students and upper secondary school students on two recently introduced standardized English tests in Sweden. Comparisons of the results are made between these two categories of students because they are entitled to compete, on an equal basis, for admission into restricted intake programs of…

  9. Perspektiv pa Las och Skrivinlarning: En Litteraturstudie som Belyser Las och Skrivinlarning utifran Fyra Teoretiska Perspektiv Samt en Instrument-Provande Barnstudie (Perspectives on Learning To Read and Write: Literature Review on Reading and Writing Acquisition through Examination of Four Theroretical Perspectives and Attitude Measures of Preschool Children).

    ERIC Educational Resources Information Center

    Fahlen, Rose-Marie

    This report focuses on the processes of learning to read and write in the initial phases. Two studies are presented. The first is a review of four theoretical approaches, including Jerome Bruner's representation theory, and theories of concept learning, metacognition, and metalinguistic awareness. The purpose of the literature study was to examine…

  10. Spectroscopy of new Sm(III) orange emitting phosphors of the type Na[Sm(SP)4], Na[Sm(WO)4] (where SP = C6H5S(O)2NP(O)(OCH3)2-; WO = CCl3C(O)NP(O)(OCH3)2-) and the polymeric materials obtained on their base

    NASA Astrophysics Data System (ADS)

    Cybińska, Joanna; Guzik, Małgorzata; Gerasymchuk, Yuriy; Trush, Victor A.; Lisiecki, Radosław; Legendziewicz, Janina

    2017-01-01

    Among a wide variety of solid state materials lanthanide beta-diketonates, their derivatives and polymeric materials based on them have become essential for advance technologies. Thus they are the subject of extensive spectroscopic studies. Using appropriate lanthanide chelates for the emission layer one can achieve electroluminescence covering the spectrum from blue to infrared. Moreover, compounds with proper chromophores can be the best way to excite and enhance the emission although the f-f transitions have forbidden character. Two types of new Sm(III) chelates; phosphoro and sulfono-derivatives of beta-diketones and polymeric materials on their base were obtained and characterized by the high resolution photoluminescence spectroscopy at 293, 77 and 4 K, as well as by luminescence decay times. Those new type of phosphors shows strong orange emission after excitation at 404 nm Sm(III) states and 280 nm ligand bands. Radiative transition probabilities were calculated from absorption spectra and Judd- Ofelt parameters evaluated. Effects of the temperature, rigidity of polymeric lattice and the energy of excitation on intensities of the Sm(III) fluorescence were studied. The paths of energy transfer are analysed and mechanism of this process is proposed.

  11. Hogskoleprovet: "En Andra Chans" Eller "Ytterligare en Oppen Dorr." Fem gymnasielarare om egna och gymnasieelevers synpunkter pa betyg och hogskoleprovet (Effects in Upper Secondary School of a More Extensive Use of the Higher Education Selection Test in the Admission to Higher Education).

    ERIC Educational Resources Information Center

    Gustavsson, Maria

    This study was designed to examine the attitudes of teachers and students in Swedish upper secondary schools in regard to the use of higher education scholastic aptitude test (SAT) scores in lieu of secondary school grades to gain entrance into higher education programs. Since 1991 applicants to higher education have been allowed to take the…

  12. CCSD(T) study of the infrared spectrum of ethyl-methyl-ether isotopic varieties

    NASA Astrophysics Data System (ADS)

    Senent, M. L.; Ruiz, R.; Villa, M.; Domínguez-Gómez, R.

    2010-02-01

    Band positions for the infrared bands of various ethyl-methyl-ether isotopomers (CH 3CH 2OCH 2D, CH 2DCH 2OCH 3, CH 3CH 2OCD 3, CD 3CH 2OCH 3, CH 3CD 2OCH 3, CH 3CH 2O 13CH 3, 13CH 3CH 2OCH 3, and CH 313CH 2OCH 3) are determined using second order perturbation theory. For species showing G18 symmetry, band position are calculated variationally from a CCSD(T)/cc-pVTZ three-dimensional potential energy surface corrected vibrationally. Potential energy barriers, fundamental frequencies, and rotational constants for excited vibrational levels, are also provided. Calculated frequencies for CH 3CH 2OCD 3 confirm experimental assignments and our predictions for the most abundant isotopomer [4].

  13. Molecular Basis for the Toxicity of Schweinfurthins to Breast Cancer cells

    DTIC Science & Technology

    2005-05-01

    OCH 3 DIPEA, OCH3 nBuLi,o OCH3 HO.MOMI MOMO geranyl bromide Br 95% Br 19 OH 20 OMOM 21 OMOM 63%j AD-mix-a, MeSO 2 NH 2 OCH3 OCH3 MOMO 1) MsCI, TEA...OH MOMO 0,, I 2) K2CO 3 , MeOH OMOM HO = OMOM 36%• F,0° [a]D = -649O 2250%)/IEDC, DMAP, OCH3 R-O-methylphenylacetic acid Ŕ OCHO Ph MOMO HO’ OH3...Gaumond, B. R.; closed in due course. Marsh, H. C. J. Med Chem. 2003, 46, 2697-2705. OMOM OMOM O=P(OEt)2 MOMO @ • MOMO . OMOM NaH, 15C5 OMOM N O1

  14. [BLOODSUCKING MOSQUITOES (DIPTERA: CULICIDAE) IN, THE TULA REGION ARE POTENTIAL VECTORS OF DIROFILARIAS].

    PubMed

    Bogacheva, A S; Ganushkina, L A; Lopatina, Yu V

    2015-01-01

    Bloodsucking mosquitoes were collected in Tula and its Region in May to August 2013-2014. The fauna included 17 species from 5 genera in the subfamily Culicinae and Anopheles maculipennis complex in the subsystem Anophelinae. Ochlerotatus cantans was a dominant species in the collections. The dominant species also included Aedes einereus, Ae. vexans, Ae. geniculatus, Och. diantaeus, Och. intrudens, Och. Cataphylla, and Culex pipiens. The possible value of different mosquito species Dirofilaria repens and D. immitis as vectors of dirofilarasis was discussed.

  15. Improving Domain-specific Machine Translation by Constraining the Language Model

    DTIC Science & Technology

    2012-07-01

    of greater amounts of training data in the two models, especially in the target language model (Brants et al., 2007). Och (2005) reports findings...train with the largest language models (NIST, 2006). The highest scoring Arabic-English system used a 1-trillion-word language model ( Och , 2006...References Brants, T.; Popat, A. C.; Xu, P.; Och , F. J.; Dean, J. Large Language Models in Machine Translation. Joint Meeting of the Conference on Empirical

  16. Fluid inclusions in the system H sub 2 O-CH sub 4 -NaCl-CO sub 2 from metasomatic tourmaline within the border unit of the Tanco zoned granitic pegmatite, S. E. Manitoba

    SciTech Connect

    Thomas, A.V.; Spooner, E.T. )

    1988-05-01

    Fluid inclusions from the tourmaline phase of alteration of the footwall amphibolite from the Tanco zoned granitic pegmatite lie in the system H{sub 2}O-CH{sub 4}-NaCl-CO{sub 2}. These inclusions contain a liquid and vapor phase at room temperature and develop a second liquid phase on cooling in the range {minus}77 to {minus}95{degree}C: the second liquid and the vapor are methane. Isochores for inclusions showing vapor phase (CH{sub 4}) homogenization were constructed from the equations of Jacobs and Kerrick (1981). The intersections of these isochores with the univariant melting curves for methane clathrate hydrates give estimates of salinity for the inclusions of between 7 and 10 equivalent wt.% NaCl, which are lower than those derived from measurement of the depression of the melting point of ice; a result consistent with salt exclusion by clathrate. The bulk composition of the fluid is estimated to be 91 mol.% H{sub 2}O, 6 mol.% CH{sub 4}, 2 equiv. mol.% NaCl and <1 mol.% CO{sub 2}. Total homogenization temperatures have a mean value of 371{degree}C {plus minus} 36{degree}C. Calculation of f{sub O2} from the bulk inclusion composition gives values near WI at these conditions which is unreasonably low for fluids derived from the pegmatite, which were probably between QFM and HM. The metasomatic fluids may have resulted from fluid mixing in the wall rock immediately adjacent to the pegmatite. The fluid derived from the pegmatite, a H{sub 2}O-CO{sub 2} fluid, introduced the B necessary to form tourmaline in the amphibolite. Supporting evidence is provided by pegmatite wall zone fluids with higher CH{sub 4} than the bulk of the pegmatite H{sub 2}O-CO{sub 2} fluids, suggesting marginal fluid contamination.

  17. Characterisation of temperature-dependent phase transitions in 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazene, N3P3Cl4[O(CH2)3O].

    PubMed

    Coles, Simon J; Davies, David B; Hursthouse, Michael B; Huth, Susanne L; Kiliç, Adem; Light, Mark E; Odlyha, Marianne; Rutherford, John S; Shaw, Robert A; Uslu, Aylin

    2007-07-18

    The crystal structure of 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclo triphosphazene has been determined at 120, 274 and 293 K. The result at 293 K confirms the room temperature Cmc2(1) structure, but at the lower temperatures the space group is Pna2(1). Nevertheless the basic structure remains the same, with only small displacements of the atoms, amounting to an average of 25 pm between 120 and 293 K. X-ray diffraction and DSC results indicate that the phase transition takes place in two steps between 274 - 293 K and provides an understanding of previous NQR results. In the intermediate temperature range the molecules are displaced from their room temperature positions in such a way as to give an average structure with Cmc2(1) symmetry. The overall phase transition is consistent with the occurrence of a soft lattice mode at room temperature in which a large displacement of the molecule in the x-direction is coupled with a flexing motion about an axis defined by the nitrogen atoms in the N1 and N3 positions.

  18. Larande I Produktionssytem. En studie av operatorsarbete i hogautomatiserad process--och verkstadsindustri = Learning in Production Systems. A Study of Operator Work in Highly Automated Process and Manufacturing Industry. Linkoping Studies in Education and Psychology, No. 63.

    ERIC Educational Resources Information Center

    Davidson, Bo; Svedin, Per-Olof

    This study of the conditions of developmental on-the-job training and learning for operators in highly automated industries is written in Swedish but contains an English abstract and 18-page summary. The summary begins with the study objectives, which were to determine the following: (1) conditions of developmental on-the-job learning in highly…

  19. Theoretical study of the mechanisms and kinetics of the reactions of hydroperoxy (HO2) radicals with hydroxymethylperoxy (HOCH2O2) and methoxymethylperoxy (CH3OCH2O2) radicals.

    PubMed

    Shao, Youxiang; Hou, Hua; Wang, Baoshan

    2014-11-07

    The reactions of hydroperoxy radicals with hydroxymethylperoxy and methoxymethylperoxy radicals were studied using the hybrid density functional theory and the coupled-cluster theory with complete basis set extrapolation. In contrast with the unsubstituted alkylperoxy reactions, it was found that OH-substitution has a significant effect on the reaction mechanism. Several hydrogen bonding reaction precursors exist at the start of the reaction. The reaction pathways show a strongly anisotropic character. The preferred transition states are four-, five-, six-, or seven-membered cyclic structures. The predicted rate coefficients are expressed as k(T) = 8.48 × 10(-24)T(3.55)e(2164/T) + 2.37 × 10(-29)T(4.70)e(3954/T) cm(3) molecule(-1) s(-1). Based on the available experimental data in the temperature range 275-333 K, the theoretical and experimental results are in agreement with a relative average deviation of only 8%. The nascent products at low and high temperatures are hydroperoxide molecules and hydroxyl radicals, respectively. A potential source has been found for the production of formic acid and new insights into the experimental observations are presented.

  20. Highly Selective Sensing of Li(+) in H2O/CH3CN via Fluorescence 'Turn-on' Response of a Coumarin-Indole Linked Dyad: an Experimental and Theoretical Study.

    PubMed

    Kumari, Santosh; Joshi, Sunita; Sarmah, Amrit; Pant, Debi; Sakhuja, Rajeev

    2016-11-01

    A coumarin-indole dyad, N-((7-hydroxy-2-oxo-2H-chromen-4-yl)methyl)-1H-indole-2-carboxamide has been synthesized and characterized by (1)H-NMR and (13)C-NMR. Effect of various metal ions on fluorescent behavior was also studied. The synthesized compound showed remarkable specificity towards Li(+) in organo-aqueous medium over other metal ions. Coordination of the compound with Li(+) induces a turn-on fluorescence response. The sensor exhibited good binding constant and low detection limit towards Li(+). Experimental results have been verified with Density Functional Theory and Time Dependent Density Functional Theory calculations.

  1. Oxo Complexes of Tungstenocene via Oxidation of (W(Eta(5)-C5H5)2(OCH3) (CH3)) and Related Reactions: Synthesis, Structural Characterization, and Photodisproportionation of the Spin Paired d(1)-d(1) Oxo Bridged Dimer ((W(Eta(5)-C5H5)2(CH3))2(Mu-O))2(+) and Synthesis and Charaterization of the d(0) Terminal Oxo Complex (W(Eta(5)-C5H5)2(O)(CH3))(+)

    DTIC Science & Technology

    1993-02-15

    work was supported in part by the Office of Na\\ al Research We thank Dr . Steven Geib and Professor Bruce Foxman for helpful discusions of the X-ra...techniques or a Vacuum Atmospheres dr % box under an atmosphere of prepunfied nitrogen unless otherise noted Glass%%are wvas flame dncd under vacuum or...of Naval Research (2)" Dr . Richard W. Drisko (1) Chemistry Division, Code 1113 Naval Civil Engineering 800 North Quincy Street Laboratory Arlington

  2. ORGANONICKEL CHEMISTRY IN THE CATALYTIC HYDRODECHLORINATION OF POLYCHLOROBIPHENYLS (PCBS): LIGAND STERIC EFFECTS AND MOLECULAR STRUCTURE OF REACTION INTERMEDIATES. (R823526)

    EPA Science Inventory

    Abstract

    Soluble homogeneous organophosphorus¯¯nickel complexes have been used to detoxify polychlorinated biphenyls (PCBs) by catalyzed hydrodechlorination using NaBH2(OCH2CH2OCH3)2 as the hyd...

  3. High Power Large Aperture Radar Methods for Meteor Observations

    DTIC Science & Technology

    2002-10-18

    the annual Swedish radio science conference RVK-02 (Radio Vetenskap och Kommunikation ) in Stockholm and at XXVIIth URSI General Assembly, Maastricht...Distribution Measurements with the EISCAT and Arecibo HPLA Radars, RVK-02 (RadioVetenskap och Kommunikation ) proceedings, 97-100, 2002. (5) Janches, D

  4. ORGANONICKEL CHEMISTRY IN THE CATALYTIC HYDRODECHLORINATION OF POLYCHLOROBIPHENYLS (PCBS): LIGAND STERIC EFFECTS AND MOLECULAR STRUCTURE OF REACTION INTERMEDIATES. (R823526)

    EPA Science Inventory

    Abstract

    Soluble homogeneous organophosphorus¯¯nickel complexes have been used to detoxify polychlorinated biphenyls (PCBs) by catalyzed hydrodechlorination using NaBH2(OCH2CH2OCH3)2 as the hyd...

  5. COMPONENTS OF SURFACE AND SUBSURFACE CONNECTIVITY IN A LARGE OREGON (USA) RIVER--WHAT CAN BE RESTORED?

    EPA Science Inventory

    We conducted research on the Willamette River in western Oregon (USA) to determine the ecological functions of off-channel habitats (OCH). OCHs have declined in our 70 km study reach of the active floodplain since European settlement. Surface and subsurface connectivity between...

  6. Fluoxetine Hydrochloride Enhances In Vitro Susceptibility to Chloroquine in Resistant Plasmodium falciparum

    DTIC Science & Technology

    1992-12-01

    chloroquine- (12), ketotifen (1), tetrandrine (20, 21), and cyproheptadine susceptible clone D6 (50% inhibitory concentration [IC 5o], (16). !s3 ng/ml). IC... CYPROHEPTADINE KETOTIFEN N OCN3 HICO N ’IN ~~OCH3 NN H 0 OCH.3 TETRANDRINE FIG. 1. Structures of fluoxetine and other drugs that have been reported to

  7. Ecological Functions of Off-Channel Habitats of the Willamette River, Oregon, Database and Documentation (1997-2001)

    EPA Science Inventory

    The database from the Ecological Functions of Off-Channel Habitats of the Willamette River, Oregon project (OCH Project) contains data collected from 1997 through 2001 from multiple research areas of the project, and project documents such as the OCH Research Plan, Quality Assura...

  8. Discourse Markers in Chinese Conversational Narrative

    ERIC Educational Resources Information Center

    Xiao, Yang

    2010-01-01

    This study examines the indexicality of discourse markers (DMs) in Chinese conversational narrative. Drawing upon theoretical and methodological principles related to narrative dimensions (Ochs & Capps, 2001), narrative desires (Ochs, 1997, 2004), and narrative positioning (Bamberg, 1997), this work proposes an integrated analytical framework for…

  9. Ecological Functions of Off-Channel Habitats of the Willamette River, Oregon, Database and Documentation (1997-2001)

    EPA Science Inventory

    The database from the Ecological Functions of Off-Channel Habitats of the Willamette River, Oregon project (OCH Project) contains data collected from 1997 through 2001 from multiple research areas of the project, and project documents such as the OCH Research Plan, Quality Assura...

  10. A new species of Aedes Meigen subgenus Ochlerotatus Lynch Arribálzaga (Diptera: Culicidae) from the coastal wetlands of the desert in northern Chile: morphological and molecular identification.

    PubMed

    González, Christian R; Reyes, Carolina; Rada-Chaparro, Viviana; Saldarriaga-Córdoba, Mónica

    2017-06-01

    Aedes (Ochlerotatus) sallumae González & Reyes n. sp. is described and validated using morphological characters of the adult male and female, male genitalia and immature stages, and its cytochrome oxidase unit 1 mitochondrial gene sequence (COI). Aedes (Och.) sallumae is morphologically close to Ae. (Och.) albifasciatus (Macquart). However, these species can be distinguished based on characters of the males and females, male genitalia and fourth-instar larvae. Aedes (Och.) sallumae was collected in the geographically isolated desert zone of northern Chile, the Atacama Desert. This isolation suggests allopatric speciation, with Ae. (Och.) sallumae divergent from its sister species Ae. (Och.) albifasciatus. Molecular characterization showed a difference of more than 8% between these species, supporting their recognition as different species.

  11. Atmospheric photooxidation of fluoroacetates as a source of fluorocarboxylic acids.

    PubMed

    Blanco, M B; Bejan, I; Barnes, I; Wiesen, P; Teruel, Mariano A

    2010-04-01

    A 1080 L environmental chamber with in situ FTIR spectroscopy detection was used to study the product distribution and the mechanism of the Cl-initiated photooxidation of a series of fluoroacetates. The gas-phase reactions of Cl atoms with ethyl trifluoroacetate (CF(3)C(O)OCH(2)CH(3)), methyl trifluoroacetate (CF(3)C(O)OCH(3)), and methyl difluoroacetate (CF(2)HC(O)OCH(3)) were investigated at 296 +/- 2 K and atmospheric pressure (approximately 760 Torr) of synthetic air. The fate of the fluoroalkoxy radicals formed in the reaction with Cl atoms mainly occurs through (i) an H-atom abstraction by reaction with O(2,) to produce the corresponding fluoroanhydride and (ii) an alpha-ester rearrangement via a five-membered ring intermediate to give the corresponding fluoroacetic acid. The yields of fluoroacids (CF(2)XC(O)OH, with X = H, F) obtained were as follows: 78 +/- 5, 23 +/- 2, and 30 +/- 5% for CF(3)C(O)OCH(2)CH(3), CF(3)C(O)OCH(3), and CF(2)HC(O)OCH(3,), respectively. Yields of OCH(2)CH(3), CF(3)C(O)OCH(3), and CF(2)HC(O)OCH(3), respectively. Formation of CF(2)O, with yield of 13 +/- 2% has been observed for the reaction of Cl with CF(2)HC(O)OCH(3). The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the radicals formed in the oxidation, that is, reaction with O(2), alpha-ester rearrangement and a decomposition pathway. The stability of the five-membered transition state of the alpha-ester rearrangement is correlated with the acid yields observed for the different fluoroacetates. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, are discussed.

  12. Analysis of HO2 and OH formation mechanisms using FM and UV spectroscopy in dimethyl ether oxidation.

    PubMed

    Suzaki, Kotaro; Tsuchiya, Kentaro; Koshi, Mitsuo; Tezaki, Atsumu

    2007-05-17

    Product formation pathways in the photolytically initiated oxidation of CH3OCH3 have been investigated as a function of temperature (298-600 K) and pressure (20-90 Torr) through the detection of HO2 and OH using Near-infrared frequency modulation spectroscopy, as well as the detection of CH3OCH2O2 using UV absorption spectroscopy. The reaction was initiated by pulsed photolysis with a mixture of Cl2, O2, and CH3OCH3. The HO2 and OH yield is obtained by comparison with an established reference mixture, including CH3OH. The CH3OCH2O2 yield is also obtained through the procedure of estimating the CH3OCH2O2/HO2 ratio from their UV absorption. A notable finding is that the OH yield is 1 order of magnitude larger than those known in C2 and C3 alkanes, increasing from 10% to 40% with increasing temperature. The HO2 yield increases gradually until 500 K and sharply up to 40% over 500 K. The CH3OCH2O2 profile has a prompt rise, followed by a gradual decay whose time constant is consistent with slow HO2 formation. To predict species profiles and yields, simple chlorine-initiated oxidation model of DME under low-pressure condition was constructed based on the existing model and the new reaction pathways, which were derived from this study. To model rapid OH formation, OH direct formation from CH3OCH2 + O2 was required. We have also proposed that a new HCO formation pathway via QOOH isomerization to HOQO species and OH + CH3OCH2O2 --> HO2 + CH3OCH2O are to be considered, to account for the fast and slow HO2 formations, as well as the total yield. The constructed model including these new pathways has successfully predicted experimental results throughout the entire temperature and pressure ranges investigated. It was revealed that the HO2 formation mechanism changes at 500 K, i.e., HCO + O2 via HCHO + OH and the above proposed direct HCO formation dominates over 500 K, while a series of reactions following CH3OCH2O2 self-reaction and OH + CH3OCH2O2 reaction mainly contribute

  13. Tin(II) alkoxide hydrolysis products for use as base catalysts

    DOEpatents

    Boyle, Timothy J.

    2002-01-01

    Tin alkoxide compounds are provided with accessible electrons. The compounds are a polymeric tin alkoxide, [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n, and the hydrolysis products Sn.sub.6 O.sub.4 (OCH.sub.2 C(CH.sub.3).sub.3).sub.4 and Sn.sub.5 O.sub.2 (OCH.sub.2 C(CH.sub.3).sub.3).sub.6. The hydrolysis products are formed by hydrolyzing the [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n in a solvent with controlled amounts of water, between 0.1 and 2 moles of water per mole of the polymeric tin alkoxide.

  14. GSFC_20170308_2017-8679_041

    NASA Image and Video Library

    2017-03-08

    Lt. Governor Rutherford and staff visited Goddard on March 8, 2017. They toured James Webb Space Telescope with Bill Ochs and Robotics Operations Center with Ben Reed. They also met John Mather, Nobel Prize winner.

  15. GSFC_20170308_2017-8679_036

    NASA Image and Video Library

    2017-03-08

    Lt. Governor Rutherford and staff visited Goddard on March 8, 2017. They toured James Webb Space Telescope with Bill Ochs and Robotic Operations Center with Ben Reed. They also met John Mather, Nobel Prize winner.

  16. GSFC_20170308_2017-8679_015

    NASA Image and Video Library

    2017-03-08

    Lt. Governor Rutherford and staff visited Goddard on March 8, 2017. They toured James Webb Space Telescope with Bill Ochs and Robotic Operations Center with Ben Reed. They also met John Mather, Nobel Prize winner.

  17. James Webb Space Telescope (JWST) Town Hall - Panel question and

    NASA Image and Video Library

    2016-11-02

    James Webb Space Telescope (JWST) Town Hall - Panel question and answer - Bill Ochs; Dr. John Mather; Dr. Eric Smith; Thomas Zurbuchen; Center Director Chris Scolese; NASA Administrator Charlie Bolden.

  18. Theoretical Investigation of Mechanisms for the Gas-Phase Unimolecular Decomposition of DMMP

    NASA Astrophysics Data System (ADS)

    Yang, Li; Shroll, Robert M.; Zhang, Jiaxu; Lourderaj, U.; Hase, William L.

    2009-11-01

    All species involved in the multichannel decomposition of gas-phase dimethyl methylphosphonate (DMMP) were investigated by electronic structure calculations. Geometries for stationary structures along the reaction paths, were fully optimized with the MP2 method and the B3LYP and MPW1K DFT functionals, and the 6-31G*, 6-31++G**, and aug-cc-pVDZ basis sets. The geometries determined by the B3LYP and MPW1K functionals are in very good agreement with the MP2 values. Increasing the basis set size from 6-31G* to aug-cc-pVDZ does not significantly alter this result. Single point energy calculations were carried out with highly accurate but computationally more expensive CBS-QB3 theory. DMMP has three conformers, which lead to the four primary product channels, (O)P(CH2)(OCH3) + CH3OH, (O)P(CH3) (OCH3)(OH) + CH2, c-(O)P(CH3)OCH2 + CH3OH, and (O)P(CH3)(OCH3)(OCH) + H2. The first channel has the lowest energy barrier and is expected to be the most important pathway. It occurs via C-H and P-O bond cleavages accompanied by O-H bond formation. The other three channels have higher and similar energy barriers, and are expected to have smaller and similar rates. The product (O)P(CH3)(OCH3)(OCH) undergoes a secondary decomposition to form (OH)P(CH3)(OCH3) + CO.

  19. α-1,6-Mannosylation of N-Linked Oligosaccharide Present on Cell Wall Proteins Is Required for Their Incorporation into the Cell Wall in the Filamentous Fungus Neurospora crassa▿†

    PubMed Central

    Maddi, Abhiram; Free, Stephen J.

    2010-01-01

    The enzyme α-1,6-mannosyltransferase (OCH-1) is required for the synthesis of galactomannans attached to the N-linked oligosaccharides of Neurospora crassa cell wall proteins. The Neurospora crassa och-1 mutant has a tight colonial phenotype and a defective cell wall. A carbohydrate analysis of the och-1 mutant cell wall revealed a 10-fold reduction in the levels of mannose and galactose and a total lack of 1,6-linked mannose residues. Analysis of the integral cell wall protein from wild-type and och-1 mutant cells showed that the mutant cell wall had reduced protein content. The och-1 mutant was found to secrete 18-fold more protein than wild-type cells. Proteomic analysis of the proteins released by the mutant into the growth medium identified seven of the major cell wall proteins. Western blot analysis of ACW-1 and GEL-1 (two glycosylphosphatidylinositol [GPI]-anchored proteins that are covalently integrated into the wild-type cell wall) showed that high levels of these proteins were being released into the medium by the och-1 mutant. High levels of ACW-1 and GEL-1 were also released from the och-1 mutant cell wall by subjecting the wall to boiling in a 1% SDS solution, indicating that these proteins are not being covalently integrated into the mutant cell wall. From these results, we conclude that N-linked mannosylation of cell wall proteins by OCH-1 is required for their efficient covalent incorporation into the cell wall. PMID:20870880

  20. Cholesteric Liquid Crystal Glass Platinum Acetylides

    DTIC Science & Technology

    2014-06-01

    have the formula trans-Pt(PR3)(cholesterol (3 or 4)- ethynyl benzoate)(1-ethynyl-4-X- benzene ), where R = Et, Bu or Oct and X = H, F, OCH3 and CN. A...have the formula trans-Pt(PR3)(cholesterol (3 or 4)-ethynyl benzoate)(1-ethynyl-4- X- benzene ), where R = Et, Bu or Oct and X = H, F, OCH3 and CN. A

  1. Perspectives on Pentaerythritol Tetranitrate (PETN) Decomposition

    SciTech Connect

    Chambers, D; Brackett, C; Sparkman, D O

    2002-07-01

    This report evaluates the large body of work involving the decomposition of PETN and identifies the major decomposition routes and byproducts. From these studies it becomes apparent that the PETN decomposition mechanisms and the resulting byproducts are primarily determined by the chemical environment. In the absence of water, PETN can decompose through the scission of the O-NO{sup 2} bond resulting in the formation of an alkoxy radical and NO{sub 2}. Because of the relatively high reactivity of both these initial byproducts, they are believed to drive a number of autocatalytic reactions eventually forming (NO{sub 2}OCH{sub 2}){sub 3}CCHO, (NO{sub 2}OCH{sub 2}){sub 2}C=CHONO{sub 2}, NO{sub 2}OCH=C=CHONO{sub 2}, (NO{sub 2}OCH{sub 2}){sub 3}C-NO{sub 2}, (NO{sub 2}OCH{sub 2}){sub 2}C(NO{sub 2}){sub 2}, NO{sub 2}OCH{sub 2}C(NO{sub 2}){sub 3}, and C(NO{sub 2}){sub 4} as well as polymer-like species such as di-PEHN and tri-PEON. Surprisingly, the products of many of these proposed autocatalytic reactions have never been analytically validated. Conversely, in the presence of water, PETN has been shown to decompose primarily to mono, di, and tri nitrates of pentaerythritol.

  2. Enhancement of the Gene Targeting Efficiency of Non-Conventional Yeasts by Increasing Genetic Redundancy

    PubMed Central

    Chen, Zao; Sun, Hongbing; Li, Pengfei; He, Ning; Zhu, Taicheng; Li, Yin

    2013-01-01

    In contrast to model yeasts, gene targeting efficiencies of non-conventional yeasts are usually low, which greatly limits the research and applications of these organisms. In this study, we aimed to enhance the gene targeting efficiency of non-conventional yeasts by improving the fitness of mutant strains, particularly by increasing the genetic redundancy of host cells. To demonstrate this process, OCH1 gene deletion in Pichia pastoris was performed. Extra copies of the OCH1 gene on a helper plasmid were provided for the P. pastoris GS115 strain before the native OCH1 gene in the genomic DNA was knocked out. The redundancy in OCH1 gene significantly eliminated the growth defects of the och1 mutant and increased the deletion efficiency of the OCH1 gene by two orders of magnitude with the same length of homologous flanks. The same strategy was used to delete the KU70 and SGS1 genes. The targeting efficiencies of KU70 and SGS1 were increased by 1- and 23-fold, respectively. Therefore, this study provided an efficient strategy for the deletion of “stubborn” genes in non-conventional yeasts. This study further showed that cellular fitness is potentially an important factor that can limit the efficiency of gene targeting. PMID:23505447

  3. Improved oral bioavailability of 20(R)-25-methoxyl-dammarane-3β, 12β, 20-triol using nanoemulsion based on phospholipid complex: design, characterization, and in vivo pharmacokinetics in rats

    PubMed Central

    Zhang, Xiangrong; Zhang, Yi; Guo, Shuang; Bai, Feifei; Wu, Tong; Zhao, Yuqing

    2016-01-01

    The aim of the study was to improve the oral absorption of the compound 25-OCH3-PPD with poor hydrophilicity and lipophilicity. 25-OCH3-PPD-phospholipid complex was prepared by solvent evaporation, then characterized by differential scanning calorimetry, scanning electron microscopy, and infrared absorption spectroscopy. The aqueous solubility and oil–water partition coefficient were compared with the free compound. A nanoemulsion loaded with 25-OCH3-PPD-phospholipid complex was developed by dissolving the complex in water in the presence of hydrophilic surfactant under sonication. After oral administration of the nanoemulsion and the suspension of 25-OCH3-PPD in rats, the concentrations of 25-OCH3-PPD in plasma were determined by high-performance liquid chromatography–tandem mass spectrometry method. The results showed that the solubility of the complex in water and n-octanol was enhanced. The oil–water partition coefficient improved 1.7 times. Peak plasma concentration and area under the curve(0–24 h) of the nanoemulsion of 25-OCH3-PPD-phospholipid complex were higher than that of free compound by 3.9- and 3.5-folds. PMID:27877020

  4. Synthesis, physicochemical analysis of two new hemilabile ether-phosphine ligands and their first stable bis-ether-phosphine/cobalt(II) tetrahedral complexes

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Barakat, Assem

    2017-04-01

    New tridentate ether-phosphine {P, 2O} and ether-phosphine oxide {OP, 2O} ligands with P and O donor-atoms have been synthesized starting from ClCH2CH(OCH3)2. The oxidation process of Ph2PCH2CH(OCH3)2 to its oxide derivative Ph2P(dbnd O)CH2CH(OCH3)2 was monitored by 31P NMR for the first time. The desired ligands and their Co(II) complexes structures were deduced from IR, EA, MS, NMR, UV-Vis., TG/DTG and XRD physical measurements. The tridentate chelating coordination behavior of the ether-phosphine wasn't detected leading only to the mono-dentate coordination mode through the phosphorous atoms to set up a X2Co[η1-Ph2PCH2CH(OCH3)2]2 as final isomer formula (X = Cl or Br). The Cl2Co[η1-Ph2PCH2CH(OCH3)2]2 isomer belongs to complex 1 was supported by single crystal measurement. Polar/non-polar intermolecular short contacts were detected by XRD and Hirshfeld surface theoretical analysis.

  5. A simple synthetic route to polyoxovanadate-based organic-inorganic hybrids using EEDQ as an ester coupling agent.

    PubMed

    Bayaguud, Aruuhan; Li, JianDa; She, Shan; Wei, Yongge

    2017-04-05

    A reaction strategy for the post-functionalization of hexavanadate derivatives is presented herein. In this study, five polyoxovanadate-based organic-inorganic hybrids TBA2[V6O13{(OCH2)3CCOO(CH2)15CH3}2] (2), TBA2[V6O13{(OCH2)3CCOO(CH2)8CH[double bond, length as m-dash]CH2}2] (3), TBA2[V6O13{(OCH2)3CCOOCH2CF3}2] (4), TBA2[V6O13{(OCH2)3CCOO(CH2CH2O)3CH3}2] (5), and TBA2[V6O13{(OCH2)3CCOO(CH2)12OH}2]·2CH3CH2OH (6) were successfully synthesized via esterification of carboxylic acid groups-containing TBA2[V6O13{(OCH2)3CCOOH}2] (1) with five alcohols possessing different functional groups. These hybrids were characterized by single crystal X-ray diffraction, IR, ESI-MS, (1)H and (13)C-NMR spectroscopies, and elemental analysis. Moreover, the formation of large vesicles was observed in a mixed solution of compound 2 due to its surfactant-like structure.

  6. Fluid inclusion volatile analysis by gas chromatography with photoionization/micro-thermal conductivity detectors: Applications to magmatic MoS sub 2 and other H sub 2 O-CO sub 2 and H sub 2 O-CH sub 4 fluids

    SciTech Connect

    Bray, C.J.; Spooner, E.T.C. )

    1992-01-01

    Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated on-line crushing, helium carrier gas, a single porous polymer column, two temperature programmed conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID), and off-line digital peak processing. In order of retention time these volatile peaks are: N{sub 2}, Ar, CO, CH{sub 4}, CO{sub 2}, C{sub 2}H{sub 4}, C{sub 2}H{sub 6}, C{sub 2}H{sub 2}, COS, C{sub 3}H{sub 6}, C{sub 3}H{sub 8}, C{sub 3}H{sub 4} (propyne), H{sub 2}O, SO{sub 2} {plus minus} iso-C{sub 4}H{sub 10} {plus minus} C{sub 4}H{sub 8} (1-butene) {plus minus} CH{sub 3}SH, C{sub 4}H{sub 8} (iso-butylene), ( ) C{sub 4}H{sub 6} (1,3 butadiene), and {plus minus} n-C{sub 4}H{sub 10} {plus minus}C{sub 4}H{sub 8} (trans-2-butene). H{sub 2}O is analyzed directly. O{sub 2} can be analyzed cryogenically between N{sub 2} and Ar, but has not been detected in natural samples to date in this study. Initial inclusion volatile analyses of fluids of interpreted magmatic origin from the Cretaceous Boss Mtn. monzogranite stock-related MoS{sub 2} deposit, central British Columbia of 97 mol% H{sub 2}O, 3% CO{sub 2}, 140-150 ppm N{sub 2}, and 16-39 ppm CH{sub 4} are reasonable in comparison with high temperature volcanic gas analyses from four, active calc-alkaline volcanoes, e.g., the H{sub 2}O contents of volcanic gases from the White Island (New Zealand), Mount St. Helens (Washington, USA), Merapi (Bali, Indonesia), and Momotombo (Nicaragua) volcanoes are 88-95%, > 90%, 88-95% and 93%, respectively; CO{sub 2} contents are 3-10%, 1-10%, 3-8%, and 3.5%. It appears that low, but significant concentrations of alkanes, alkenes, and alkynes have been detected in magmatically derived fluids.

  7. Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

    PubMed

    Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

    2014-11-20

    Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

  8. Electrochemical storage cell containing a substituted anisole or di-anisole redox shuttle additive for overcharge protection and suitable for use in liquid organic and solid polymer electrolytes

    SciTech Connect

    Kerr, John B.; Tian, Minmin

    1998-12-01

    A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte; and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula shown in a figure (in an uncharged state): where R{sub 1} is selected from the group consisting of H, 0CH{sub 3}, OCH{sub 2}CH{sub 3}, and OCH{sub 2}phenyl, and R{sub 2} is selected from the group consisting of OCH{sub 3}, OCH{sub 2}CH{sub 3}, OCH{sub 2} phenyl, and O{sup {minus}}Li{sup +}; and (b) a di-anisole compound having the general formula shown in a second figure (in an uncharged state): where R is selected from the group consisting of -OCH{sup 3} and -CH{sub 3}, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH{sub 3} (methoxy) or its lithium salt -O{sup {minus}}Li{sup +}. The lithium salt of the di-anisole is the preferred form of the redox shuttle additive because the shuttle anion will then initially have a single negative charge, it loses two electrons when it is oxidized at the cathode, and then moves toward the anode as a single positively charged species where it is then reduced to a single negatively charged species by gaining back two electrons.

  9. Hydroxyl end groups influence in vibrational and transport properties in polymer/monomer solutions: the PEO/EG case

    NASA Astrophysics Data System (ADS)

    Crupi, V.; Faraone, A.; Majolino, D.; Migliardo, P.; Venuti, V.; Villari, V.

    A study has been made of vibrational properties in ethylene glycol (EG; H(OCH2CH2)OH) and EG monomethyl ether (EGmE; CH3(OCH2CH2)OH) in solution together with poly(ethylene oxide) (PEO; H(OCH2CH2)nOH) at different concentrations, performed by Fourier transform infrared absorbance (FT-IR) spectroscopy. The results ae compared with previous viscometry and photon correlation spectroscopy (PCS) studies, using EG dimethyl ether (EGdE; CH3(OCH2CH2)OCH3) as solvent as well. These homologous systems differ from each other in the number of OH end groups, in particular two for EG, one for EgmE and zero for EGdE. Combining analysis of the vibrational and transport properties of EG, EGmE and EGdE in solution with PEO over a wide range of concentration made it possible to check the quality (good theta or poor) of these three different solvents and the role played by the hydrogen bond in the various solute-solvent interaction mechanisms, resulting in the well known de Gennes scaling law.

  10. Structural basis for piRNA 2'-O-methylated 3'-end recognition by Piwi PAZ (Piwi/Argonaute/Zwille) domains.

    PubMed

    Tian, Yuan; Simanshu, Dhirendra K; Ma, Jin-Biao; Patel, Dinshaw J

    2011-01-18

    Argonaute and Piwi proteins are key players in the RNA silencing pathway, with the former interacting with micro-RNAs (miRNAs) and siRNAs, whereas the latter targets piwi-interacting RNAs (piRNAs) that are 2'-O-methylated (2(')-OCH(3)) at their 3' ends. Germline-specific piRNAs and Piwi proteins play a critical role in genome defense against transposable elements, thereby protecting the genome against transposon-induced defects in gametogenesis and fertility. Humans contain four Piwi family proteins designated Hiwi1, Hiwi2, Hiwi3, and Hili. We report on the structures of Hili-PAZ (Piwi/Argonaute/Zwille) domain in the free state and Hiwi1 PAZ domain bound to self-complementary 14-mer RNAs (12-bp + 2-nt overhang) containing 2(')-OCH(3) and 2'-OH at their 3' ends. These structures explain the molecular basis underlying accommodation of the 2(')-OCH(3) group within a preformed Hiwi1 PAZ domain binding pocket, whose hydrophobic characteristics account for the preferential binding of 2(')-OCH(3) over 2'-OH 3' ends. These results contrast with the more restricted binding pocket for the human Ago1 PAZ domain, which exhibits a reverse order, with preferential binding of 2'-OH over 2(')-OCH(3) 3' ends.

  11. Mechanical properties and interface characteristics of nanoporous low-k materials.

    PubMed

    Si, Lina; Guo, Dan; Xie, Guoxin; Luo, Jianbin

    2014-08-27

    Low dielectric constant (low-k) insulator films with outstanding mechanical strength and fracture resistance are needed urgently for the new generation of ultra-large-scale integrated circuits (ULSI). In this paper, the mechanical properties of low-k materials and the adhesion strengths between these materials with silica have been analyzed by using molecular dynamics (MD) simulations. Atomistic models of two kinds of representative low-k materials [nanoporous amorphous silica (n-a-SiO2) and SiOCH] and their contact models with silica have been constructed. The mechanical strength of the n-a-SiO2 film decreased with the increase of porosity, and the relationship between the normalized elastic modulus and porosity was modeled. The modulus of the SiOCH film with -CH2- groups was enhanced compared with that without -CH2- groups, and the mechanism was discussed. Through investigations of the adhesion strengths between n-a-SiO2, SiOCH, and silica, it was shown that the adhesion strengths of the n-a-SiO2/silica interfaces decreased with porosity. The adhesion strengths of the SiOCH films with both -CH2- groups and -CH3 groups were higher than that of the SiOCH film merely with -CH3 groups.

  12. Site-selective electroless metallization on porous organosilica films by multisurface modification of alkyl monolayer and vacuum plasma.

    PubMed

    Chen, Giin-Shan; Chen, Sung-Te; Chen, Yenying W; Hsu, Yen-Che

    2013-01-15

    Taking plasma-enhanced chemical vapor deposited porous SiOCH (p-SiOCH) and octadecyltrichlorosilane (OTS) as model cases, this study elucidates the chemical reaction pathways for alkyl-based self-assembled monolayers (SAMs) on porous carbon-doped organosilica films under N(2)-H(2) vacuum plasma illumination. In contrast to previous findings that carboxylic groups are found in alkyl-based SAMs only by exposure to oxygen-based plasma, this study discovers that, upon exposure to reductive nitrogen-based vacuum plasma, surface carboxylic functional groups can be instantly formed on OTS-coated p-SiOCH films. Particular attention is given to developing a multisurface modification process, starting with the modification of p-SiOCH films by N(2)-H(2) plasma and continuing with SAM deposition and plasma patterning; this ultimately leads to site-selective seeding for the spatially controlled fabrication of Cu-wire metallization by electroless deposition. Plasma diagnosis and X-ray near-edge absorption and Fourier transform infrared spectroscopies show that, by adequately controlling the plasma parameters, the bulk of the p-SiOCH films are free from plasma damage (in terms of degradation in bonding structures and electrical properties); the formation of the seed-trapping carboxylic functional groups on the surface, the key factor for the validity of this new seeding process, is due to a water-mediated chemical oxygenation route.

  13. Structural basis for piRNA 2'-O-methylated 3'-end recognition by Piwi PAZ (Piwi/Argonaute/Zwille) domains

    PubMed Central

    Tian, Yuan; Simanshu, Dhirendra K.; Ma, Jin-Biao; Patel, Dinshaw J.

    2011-01-01

    Argonaute and Piwi proteins are key players in the RNA silencing pathway, with the former interacting with micro-RNAs (miRNAs) and siRNAs, whereas the latter targets piwi-interacting RNAs (piRNAs) that are 2′-O-methylated (2′-OCH3) at their 3′ ends. Germline-specific piRNAs and Piwi proteins play a critical role in genome defense against transposable elements, thereby protecting the genome against transposon-induced defects in gametogenesis and fertility. Humans contain four Piwi family proteins designated Hiwi1, Hiwi2, Hiwi3, and Hili. We report on the structures of Hili-PAZ (Piwi/Argonaute/Zwille) domain in the free state and Hiwi1 PAZ domain bound to self-complementary 14-mer RNAs (12-bp + 2-nt overhang) containing 2′-OCH3 and 2′-OH at their 3′ ends. These structures explain the molecular basis underlying accommodation of the 2′-OCH3 group within a preformed Hiwi1 PAZ domain binding pocket, whose hydrophobic characteristics account for the preferential binding of 2′-OCH3 over 2′-OH 3′ ends. These results contrast with the more restricted binding pocket for the human Ago1 PAZ domain, which exhibits a reverse order, with preferential binding of 2′-OH over 2′-OCH3 3′ ends. PMID:21193640

  14. Unimolecular thermal decomposition of dimethoxybenzenes

    NASA Astrophysics Data System (ADS)

    Robichaud, David J.; Scheer, Adam M.; Mukarakate, Calvin; Ormond, Thomas K.; Buckingham, Grant T.; Ellison, G. Barney; Nimlos, Mark R.

    2014-06-01

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH3O-C6H4-OCH3) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH3O-C6H4-OCH3, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C6H4-CHO) and phenol (C6H5OH). Para-CH3O-C6H4-OCH3 immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C5H4=O). Finally, the m-CH3O-C6H4-OCH3 isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C5H4=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  15. Oxidative demethylation in monooxygenase model systems. Competing pathways for binuclear and helical multinuclear copper(I) complexes

    SciTech Connect

    Gelling, O.J.; Feringa, B.L. )

    1990-10-10

    The ligand 2,6-bis(N-(2-pyridylethyl)formimidoyl)-1-methoxybenzene (2,6-BPB-1-OCH{sub 3}) (4) reacts with Cu-(CH{sub 3}CN){sub 4}BF{sub 4} to form novel binuclear copper(I) complexes (Cu{sub 2}(2,6-BPB-1-OCH{sub 3})(BF{sub 4}){sub 2}(CH{sub 3}CN){sub 4}) (11) and (Cu{sub 2}(2,6-BPB-1-OCH{sub 3})(BF{sub 4}){sub 2}(CH{sub 2}Cl{sub 2}){sub 0.5}) (14), or the helical polynuclear copper(I) complex (Cu(2,6-BPB-1-OCH{sub 3})(BF{sub 4})){sub n} (16). The complexes mimic certain monooxygenases as they rapidly take up O{sub 2} followed by demethylation of the anisole moiety (up to 95% yield). {sup 18}O experiments are provided that show competing aryl-oxygen ({ge}60%) and alkyl-oxygen (20%) bond cleavage pathways. Introduction of a p-methoxy substituent in the arene moiety of complex 11 decreases the oxygenation rate and led to an unprecedented O{sub 2} induced arene-OCH{sub 3}-OCD{sub 3} exchange at 20{degree}C in CD{sub 3}OD. A mechanistic rational is given.

  16. Analysis of Wartime Consumption Rates for Chemical Defensive Equipment. Volume 3. Appendix D. Post-Processor Data

    DTIC Science & Technology

    1986-05-01

    101.18 113.96 123.0 -N-----5 CTIC CATA - 10 RMXL FO]R WVCl&A KR DAYS 1 DRDI 15 Mv% tM OF O-eiICA&L RT•M••M 25 MIL DAS FJIF FOER EKH ODY OF BATTLE OaNm 1...0.68 0.68 6.66s 0.08 0.6 AG 0.68 .0.6 0.68 6.68 0.68e 66 0. 68 0. 68 ~e 0.0 AVEVM NM. RMAIE PER DAY PER 160M ~ TM AfW I CaMrWi 1 2 3 4 5 6 7 8 MCG 2...I6 IN W3’PPLM2 FR’ T - TMS CJ1Rw 1 2 3 4 5 6 7 8 TOTAL 1 0.95 3.42 2.14 0.19 3.05 5.02 4.25 0.60 19.1 2 4.37 3.29 5.57 2.22 3.93 0.0 6.60 3.94 23.1 3

  17. Study of the OH and Cl-initiated oxidation, IR absorption cross-section, radiative forcing, and global warming potential of four C4-hydrofluoroethers.

    PubMed

    Oyaro, Nathan; Sellevåg, Stig R; Nielsen, Claus J

    2004-11-01

    Infrared absorption cross-sections and OH and Cl reaction rate coefficients for four C4-hydrofluoroethers (CF3)2CHOCH3, CF3CH2OCH2CF3, CF3CF2CH2OCH3, and CHF2CF2CH2OCH3 are reported. Relative rate measurements at 298 K and 1013 hPa of OH and Cl reaction rate coefficients give k(OH+(CF3)2CHOCH3) = (1.27+/-0.13) x 10(-13), k(OH+CF3CH2OCH2CF3) = (1.51+/-0.24) x 10(-13), k(OH+CF3CF2CH2OCH3) = (6.42+/-0.33) x 10(-13), k(OH+CHF2CF2CH2OCH3) = (8.7 +/-0.5) x 10(-13), k(Cl+(CF3)2CHOCH3) = (8.4+/-1.3) x 10(-12), k(Cl+CF3CH2OCH2CF3) = (6.5+/-1.7) x 10(-13), k(Cl+CF3CF2CH2OCH3) = (4.0+/-0.8) x 10(-11), and k(Cl+CHF2CF2CH2OCH3) = (2.65+/-0.17) x 10(-11) cm3 molecule(-1) s(-1). The primary products of the OH and Cl reactions with the fluorinated ethers have been identified as esters, and OH and Cl reaction rate coefficients for one of these, CF3CH2OCHO, are reported: k(OH+CF3CH2OCHO) = (7.7+/-0.9) x 10(-14) and kCl+CF3CH2OCHO) = (6.3+/-1.9) x 10(-14) cm3 molecule(-1) s(-1) The rate coefficient for the Cl-atom reaction with CHF2CH2F is derived as k(Cl+CHF2CH2F) = (3.0+/-0.9) x 10(-14) cm3 molecule(-1) s(-1) at 298 K. The error limits include 3sigma from the statistical data analyses as well as the errors in the rate coefficients of the reference compounds employed. The tropospheric lifetimes of the hydrofluoroethers are estimated to be short tauOH((CF3)2CHOCH3) approximately 100 days, tauOH(CF3CH2OCH2CF3) approximately 80 days, tauOH(CF3CF2CH2OCH3) approximately 20 days, and tauOH(CHF2CF2CH2OCH3) approximately 14 days, and their global warming potentials are small compared to CFC-11.

  18. Tetra­hydro­berberine, a pharmacologically active naturally occurring alkaloid

    PubMed Central

    Pingali, Subramanya; Donahue, James P.; Payton-Stewart, Florastina

    2015-01-01

    Tetra­hydro­berberine (systematic name: 9,10-dimeth­oxy-5,8,13,13a-tetra­hydro-6H-benzo[g][1,3]benzodioxolo[5,6-a]quinolizine), C20H21NO4, a widely distributed naturally occurring alkaloid, has been crystallized as a racemic mixture about an inversion center. A bent conformation of the mol­ecule is observed, with an angle of 24.72 (5)° between the arene rings at the two ends of the reduced quinolizinium core. The inter­molecular hydrogen bonds that play an apparent role in crystal packing are 1,3-benzodioxole –CH2⋯OCH3 and –OCH3⋯OCH3 inter­actions between neighboring mol­ecules. PMID:25836282

  19. Theoretical studies on atmospheric chemistry of HFE-245mc and perfluoro-ethyl formate: Reaction with OH radicals, atmospheric fate of alkoxy radical and global warming potential

    NASA Astrophysics Data System (ADS)

    Lily, Makroni; Baidya, Bidisha; Chandra, Asit K.

    2017-02-01

    Theoretical studies have been performed on the kinetics, mechanism and thermochemistry of the hydrogen abstraction reactions of CF3CF2OCH3 (HFE-245mc) and CF3CF2OCHO with OH radical using DFT based M06-2X method. IRC calculation shows that both hydrogen abstraction reactions proceed via weakly bound hydrogen-bonded complex preceding to the formation of transition state. The rate coefficients calculated by canonical transition state theory along with Eckart's tunnelling correction at 298 K: k1(CF3CF2OCH3 + OH) = 1.09 × 10-14 and k2(CF3CF2OCHO + OH) = 1.03 × 10-14 cm3 molecule-1 s-1 are in very good agreement with the experimental values. The atmospheric implications of CF3CF2OCH3 and CF3CF2OCHO are also discussed.

  20. Transparent Optical Protection Ring Architectures and Applications

    NASA Astrophysics Data System (ADS)

    Li, Ming-Jun; Soulliere, Mark J.; Tebben, Daniel J.; Nederlof, Leo; Vaughn, Mark D.; Wagner, Richard E.

    2005-10-01

    This paper reviews recent progress in optical protection rings with the focus on transparent optical protection rings. Different optical protection ring architectures, such as dedicated and shared protection rings, in both the optical-channel (OCh) layer and the optical multiplex section (OMS) layer, are described. In particular, OCh shared protection rings (OChSPRINGs) are discussed in detail including node-architecture designs, ring protocols, triggers, and messaging channels. Feasibility studies and experimental results from Corning Inc. and other companies are reviewed. The paper also discusses how protection-switching times scale with number of nodes and number of wavelengths, and shows examples of applications using the scaling rules for practical optical networks such as metro, regional, and long-haul ring networks. The cost benefits of transparent optical protection rings are analyzed using a typical metro network. Finally, the paper discusses remaining issues and future developments in the optical protection ring area.

  1. Tetrahydroberberine, a pharmacologically active naturally occurring alkaloid.

    PubMed

    Pingali, Subramanya; Donahue, James P; Payton-Stewart, Florastina

    2015-04-01

    Tetrahydroberberine (systematic name: 9,10-dimethoxy-5,8,13,13a-tetrahydro-6H-benzo[g][1,3]benzodioxolo[5,6-a]quinolizine), C20H21NO4, a widely distributed naturally occurring alkaloid, has been crystallized as a racemic mixture about an inversion center. A bent conformation of the molecule is observed, with an angle of 24.72 (5)° between the arene rings at the two ends of the reduced quinolizinium core. The intermolecular hydrogen bonds that play an apparent role in crystal packing are 1,3-benzodioxole -CH2···OCH3 and -OCH3···OCH3 interactions between neighboring molecules.

  2. End of Year Report for 1 October 1984 through 30 September 1985 for Contract Number N00014-84-K-0289,

    DTIC Science & Technology

    1985-09-30

    of LiBF4 and methoxyethyldimethyl ethyl ammonium fluoroborate - which may conduct by the same mechanism as Li 2 SO4 since it exhibits a strong disord...supplied by a The appropriate route to such a material evi- "sacrificial" portion of LiBF4 (previously dried with dently will involve a reduction in...Ttr/°C(A Htr)c Tm(4 Hm)C I MeOCH 2 CH 2 N EtMe 2 BF 4 -08 13(21.7) 2 MeOCH 2 CH 2 N 4 +EtMe 2 BF 4 - LiBF4 -79 -70(3.9)02(1.7) 98(5.6) 3 MeOCH2 CH2 N

  3. Tolerance of β-diketone hydrolases as representatives of the crotonase superfamily towards organic solvents.

    PubMed

    Siirola, Elina; Grischek, Barbara; Clay, Dorina; Frank, Annika; Grogan, Gideon; Kroutil, Wolfgang

    2011-12-01

    Crotonase superfamily enzymes catalyze a wide variety of reactions, including hydrolytic C-C bond cleavage in symmetrical β-diketones by 6-oxo camphor hydrolase (OCH) from Rhodococcus sp. The organic solvent tolerance and temperature stability of OCH and its structurally related ortholog Anabaena β-diketone hydrolase have been investigated. Both enzymes showed excellent tolerance toward organic solvents; for instance, even in the presence of 80% (v/v) THF or dioxane, OCH was still active. In most solvent mixtures, except methanol, the stereospecificity was conserved (>99% e.e. of product), hence neither the type of solvent nor its concentration appeared to have an effect on the stereoselectivity of the enzyme. Attempts to correlate the observed activities with log P, functional solvent group or denaturing capacity (DC) of the solvent were only successful in the case of DC for water miscible solvents. This study represents the first investigation of organic solvent stability for members of the crotonase superfamily.

  4. Temporal assessment of traumatic axonal injury in the rat corpus callosum and optic chiasm.

    PubMed

    Zakaria, Nisrine; Kallakuri, Srinivasu; Bandaru, Sharath; Cavanaugh, John M

    2012-07-27

    Impaired axoplasmic transport (IAT) and neurofilament compaction (NFC), two common axonal pathology processes involved in traumatic axonal injury (TAI), have been well characterized. TAI is found clinically and in animal models in brainstem white matter (WM) tracts and in the corpus callosum (CC), optic chiasm (Och), and internal capsule. Previous published quantitative studies of the time course of TAI expression induced by the Marmarou impact acceleration model have been limited to the brainstem. Accordingly, this study assessed the extent of IAT and NFC in the CC and Och at 8h, 28 h, 3 days and 7 days after traumatic brain injury (TBI) induction by the Marmarou impact acceleration model. IAT peak density was observed at 8h in the CC and 28 h in the Och post-TBI. NFC peak density was observed at 28 h in both structures. The density of IAT and NFC decreased with increasing survival time in both structures. The NFC density time profile followed a similar trend in both the Och and CC, whereas the IAT density time profile was variable between the Och and CC. Furthermore, a strong linear relationship was observed between IAT and NFC in the CC but not in the Och. These findings highlight the heterogeneity of TAI as evidenced by variable IAT and NFC injury time profiles in each anatomical structure. This variability indicates the requirement of multiple markers for a comprehensive TAI evaluation and multiple targeted treatments for TAI polypathology within its therapeutic window time frame. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. C---lH...O and O...H...O bonded intermediates in the dissociation of low energy methyl glycolate radical cations

    NASA Astrophysics Data System (ADS)

    Suh, Dennis; Kingsmill, Carol A.; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    1995-08-01

    Low energy methyl glycolate radical cations HOCH2C(=O)OCH3+, 1, abundantly lose HCO, yielding protonated methyl formate H---C(OH)OCH3+. Tandem mass spectrometry based experiments on 2H, 13C and 18O labelled isotopologues show that this loss is largely (about 75%) atom specific. Analysis of the atom connectivity in the product ions indicates that the reaction proceeds analogously to the loss of HCO and CH3CO from ionized acetol HOCH2C(=O)CH3+ and acetoin HOCH(CH3)C(=O)CH3+, respectively. The mechanism, it is proposed, involves isomerization of 1 to the key intermediate CH2=O... H---C(=O)OCH3+, an H-bridged ion-dipole complex of neutral formaldehyde and ionized methyl formate. Next, charge transfer takes place to produce CH3OC(H)=O...HC(H)=O+, an H-bridged ion-dipole complex of ionized formaldehyde and neutral methyl formate, followed by proton transfer to generate the products. Preliminary ab initio calculations executed at the UMP3/6-31G*//6-31G*+ZPVE level of theory are presented in support of this proposal. The non-specific loss of HCO from 1 (about 25%) is rationalized to occur via the same mechanism, but after communication with isomeric dimethyl carbonate ions CH3OC(=O)OCH3+, 2, via the O...H...O bonded intermediate [CH2=O...H...O=C---OCH3]+. The latter pathway is even more important in the formation of CH2OH+ ions from 1 which, it is shown, is not a simple bond cleavage reaction, but may involve consecutive or concerted losses of CH3 and CO2 from the above O...H...O bonded species. Ionized methyl lactate HOCH(CH3)C(=O)OCH3+, the higher homologue of 1, shows a unimolecular chemistry which is akin to that of 1.

  6. Influence of boron concentration on growth characteristic and electro-catalytic performance of boron-doped diamond electrodes prepared by direct current plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Feng, Yujie; Lv, Jiangwei; Liu, Junfeng; Gao, Na; Peng, Hongyan; Chen, Yuqiang

    2011-02-01

    A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH4/H2/B(OCH3)3 gas mixture. A maximum growth rate of 0.65 mg cm-2 h-1 was obtained with CH4/H2/B(OCH3)3 radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH3)3 that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH4/H2/B(OCH3)3 ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 1020 cm-3 with CH4/H2/B(OCH3)3 ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH4/H2/B(OCH3)3 ratio of 4/190/10 possessed the best phenol removal efficiency.

  7. Organic pollutant burden of the giant mussels Choromytilus chorus from the south-central Chilean coast.

    PubMed

    Toro, Beatriz; Palma-Fleming, Hernán; Navarro, Jorge M

    2004-04-01

    A comparative quantitative analysis was made on the contents of organochlorines (OCh) and polycyclic aromatic hydrocarbons (PAH) in tissues of the giant mussel Choromytilus chorus from three bays in south-central Chile exposed to various degrees of pollutant input. Mussels from the three bays contained levels of OCh near the detection limits of method, with a tendency to be slightly higher in the polluted bay (San Vicente) than in the other bays (Corral and Yaldad). PAH levels and types in Corral and Yaldad were well below of carcinogenicity permitted in mussels for human consumption.

  8. Nitroaliphatic difluoroformals

    DOEpatents

    Peters, Howard M.; Simon, Jr., Robert L.

    1978-01-01

    Nitroaliphatic difluoroformals of the formula RCH.sub.2 OCF.sub.2 OCH.sub.2 R' wherein R = FC(NO.sub.2).sub.2 -- and R' = F.sub.2 C(NO.sub.2)-- or CF.sub.3 --; or R = R' = CF.sub.3 OCH.sub.2 C(NO.sub.2).sub.2 --. The compounds are prepared in accordance with the following reaction: ##STR1## carried out at temperatures of from about 95.degree. C to about 150.degree. C. The compounds are especially useful as energetic plasticizers in explosive compositions.

  9. A rare tetranuclear thorium(IV) μ4 -oxo cluster and dinuclear thorium(IV) complex assembled by carbon-oxygen bond activation of 1,2-dimethoxyethane (DME).

    PubMed

    Travia, Nicholas E; Scott, Brian L; Kiplinger, Jaqueline L

    2014-12-15

    The synthesis and X-ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ4 -oxo cluster complex Th4 (μ4 -O)(μ-Cl)2 I6 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]6 and the dinuclear complex Th2 I5 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]3 (DME) (DME=dimethoxyethane) are formed by CO bond activation of 1,2-dimethoxyethane (DME) mediated by thorium iodide complexes.

  10. Spectroscopic characterization of the complex between water and the simplest Criegee intermediate CH2OO.

    PubMed

    Nakajima, Masakazu; Endo, Yasuki

    2014-04-07

    The hydrogen-bonded complex between water and the simplest Criegee intermediate CH2OO was detected by Fourier-transform microwave spectroscopy under a jet-cooled condition. Both a-type and b-type rotational transitions were observed for H2O-CH2OO and D2O-CH2OO. The determined rotational constants enable us to conclude that the complex has an almost planar ring structure with the terminal oxygen atom of CH2OO being a strong proton acceptor.

  11. Spectroscopic characterization of the complex between water and the simplest Criegee intermediate CH2OO

    NASA Astrophysics Data System (ADS)

    Nakajima, Masakazu; Endo, Yasuki

    2014-04-01

    The hydrogen-bonded complex between water and the simplest Criegee intermediate CH2OO was detected by Fourier-transform microwave spectroscopy under a jet-cooled condition. Both a-type and b-type rotational transitions were observed for H2O-CH2OO and D2O-CH2OO. The determined rotational constants enable us to conclude that the complex has an almost planar ring structure with the terminal oxygen atom of CH2OO being a strong proton acceptor.

  12. Stabile Radikalanionen von Aromaten: Strahlenchemische Erzeugung in Gegenwart von Natrium-dihydridobis( 2-methoxyethoxy) aluminat

    NASA Astrophysics Data System (ADS)

    Getoff, Nikola; Haenel, Matthias W.; Hildenbrand, Knut; Richter, Udo-Burckhard; Solar, Sonja

    1990-02-01

    Arenes are reduced at room temperature to their very long-lived radical anions by exposing the solution of the arene and NaAlH2(OCH2CH2OCH3 )2 (1) in dimethoxyethane (DME) to an ionizing radiation (electrons, gamma- or X-rays) for few minutes: Thereby 1 is acting as a scavenger for the solvent counter ions which are produced concomitantly to solvated electrons by the radiolysis. The method is very convenient for the ESR and UV-VIS spectroscopy of aromatic radical anions.

  13. Analysis of torsional spectra of molecules with two internal C3v rotors. II - Far infrared and low frequency Raman spectra of dimethylether isotopes

    NASA Technical Reports Server (NTRS)

    Groner, P.; Durig, J. R.

    1977-01-01

    The torsional far infrared and Raman spectra of gaseous CH3OCH3, CD3OCH3, and CD3OCD3 are presented. They are analyzed using a computer program which is based on the results of an extensive investigation of the isometric groups and of the symmetry groups of the rotation-internal rotation Hamiltonians of a series of semirigid two-top models. Four or more Fourier coefficients of the potential functions in two variables could be determined for each isotope. Strong evidence was found for Fermi-resonance-type interactions with the COC bending mode.

  14. Oral capillary hemangioma: a clinical protocol of diagnosis and treatment in adults.

    PubMed

    da Silva, Walessa Brasil; Ribeiro, André Luis Ribeiro; de Menezes, Sílvio Augusto Fernandes; de Jesus Viana Pinheiro, João; de Melo Alves-Junior, Sérgio

    2014-12-01

    Hemangiomas are benign vascular anomalies characterized by benign proliferation of blood vessels. There are no well-defined criteria for the diagnosis and treatment of oral capillary hemangioma (OCH). The objective of this study is to report a safe, effective, and low-cost protocol for diagnosis and treatment of OCH. Eight patients were diagnosed with OCH, through two physical examination maneuvers-the diascopy and head lowering maneuver with abdominal compression (HLMAC). The treatment performed was sclerotherapy with ethanolamine oleate, weekly, until the disappearance of the lesion. No local anesthetics were administered prior to the sclerosing agent injection. All cases showed a complete remission of the lesions after sclerotherapy. There were no visible scars or compromise esthetics or normal function, and there was no evidence of recurrence. Only one patient had superficial ulceration, which remained asymptomatic and healed without specific treatment. This protocol was effective in the diagnosis of OCH through two physical examination maneuvers with low-cost and easy implementation, the diascopy and the HLMAC. The low concentration associated with a reduced amount of the sclerosing agent was responsible for the excellent results in the cases treated.

  15. Adolescent Tobacco and Cannabis Use: Young Adult Outcomes from the Ontario Child Health Study

    ERIC Educational Resources Information Center

    Georgiades, Katholiki; Boyle, Michael H.

    2007-01-01

    Background: This study examines the longitudinal associations between adolescent tobacco and cannabis use and young adult functioning. Methods: Data for analysis come from the Ontario Child Health Study (OCHS), a prospective study of child health, psychiatric disorder and adolescent substance use in a general population sample that began in 1983,…

  16. Peer Socialization into Gendered L2 Mandarin Practices in a Study Abroad Context: Talk in the Dorm

    ERIC Educational Resources Information Center

    Diao, Wenhao

    2016-01-01

    This article reports on the peer socialization of gendered Mandarin practices between three American students and their Chinese roommates in a college dorm in China. Gender is often perceived to be a salient identity category among adult L2 learners overseas. Drawing on the language socialization framework (Ochs and Schieffelin 1984), this study…

  17. Co-Construction in Korean Interaction

    ERIC Educational Resources Information Center

    Ju, Hee

    2011-01-01

    This dissertation explores co-construction of a situated activity in a current unit by mainly focusing on hearers' actions. The "co-construction" involves a process of interaction in which speakers and hearers jointly construct the form and the meaning of ongoing utterances even when they disagree with each other (Jacoby & Ochs,…

  18. A Voyage through the Radio Universe

    ERIC Educational Resources Information Center

    Spuck, Timothy

    2004-01-01

    Each year, professionals and amateurs alike make significant contributions to the field of astronomy. High school students can also conduct astronomy research. Since 1992, the Radio Astronomy Research Team from Oil City Area Senior High School (OCHS) in Oil City, Pennsylvania, has traveled each year to the National Radio Astronomy Observatory…

  19. Parental Expectations of the Swedish Municipal School of Arts

    ERIC Educational Resources Information Center

    Lilliedahl, Jonathan; Georgii-Hemming, Eva

    2009-01-01

    This article draws on a study designed to analyse parental expectations of the Swedish municipal school of arts (hereafter MSA) (in Swedish: kommunal musik- och kulturskola). The study is based on in-depth interviews conducted and informed by grounded theory. Although parental expectations are scarcely uniform, the study reveals a hope that the…

  20. Social Networking in an Intensive English Program Classroom: A Language Socialization Perspective

    ERIC Educational Resources Information Center

    Reinhardt, Jonathon; Zander, Victoria

    2011-01-01

    This ongoing project seeks to investigate the impact, inside and outside of class, of instruction focused on developing learner awareness of social-networking site (SNS) use in an American Intensive English Program (IEP). With language socialization as an interpretative framework (Duff, in press; Ochs, 1988; Watson-Gegeo, 2004), the project uses a…

  1. Debate on the Draft--Helping Students Decide Where They Stand.

    ERIC Educational Resources Information Center

    Victory, James

    1981-01-01

    Presents four exercises to help secondary school social studies students understand the complex issues of the draft. Students participate in a mock draft lottery, analyze Phil Och's Draft Dodger Rag, examine how individual experiences affect attitudes, and compare writings by Bill Mauldin and Ron Kovic. (KC)

  2. Socialising ESL Students into the Discourse of School Science through Academic Writing

    ERIC Educational Resources Information Center

    Huang, Jingzi

    2004-01-01

    This paper takes the view of "language socialization" (Schieffelin & Ochs, 1986) to examine, through a case study of a secondary ESL science class, the instructional process that aims at facilitating the integration of specific science content learning and the construction of a particular kind of written discourse typically found in school…

  3. The Spoken Self: An Ethnographic Exploration of Accent and Identity

    ERIC Educational Resources Information Center

    Rehn, Stefanie

    2010-01-01

    This study examines the relationship between accent and identity in three Chinese graduate students attending a large research-one university in the northeastern United States. The study is based on Och's (1993) concept if identity as jointly constructed by the individual herself and the persons and conventions of her culture. It also examines the…

  4. Social Networking in an Intensive English Program Classroom: A Language Socialization Perspective

    ERIC Educational Resources Information Center

    Reinhardt, Jonathon; Zander, Victoria

    2011-01-01

    This ongoing project seeks to investigate the impact, inside and outside of class, of instruction focused on developing learner awareness of social-networking site (SNS) use in an American Intensive English Program (IEP). With language socialization as an interpretative framework (Duff, in press; Ochs, 1988; Watson-Gegeo, 2004), the project uses a…

  5. Schools Reaching Out: An Introduction.

    ERIC Educational Resources Information Center

    Heleen, Owen

    1990-01-01

    Introduces an issue devoted to the Schools Reaching Out projects at David A. Ellis School in Roxbury (MA) and Adolph S. Ochs School in New York City. Projects attempt to link the schools with parents and their communities to promote the students' academic and social success. (DM)

  6. Legitimate Peripheral Participation and Language Learning: Two Quichua Learners in a Transnational Community

    ERIC Educational Resources Information Center

    Back, Michele

    2011-01-01

    Using data from a multisited ethnography of Ecuadorian transnational musicians, I applied Lave and Wenger's (1991) concept of legitimate peripheral participation and Jacoby and Ochs's (1995) notion of co-construction to examine two musicians' attempts to learn Quichua, an Ecuadorian indigenous language. Through an analysis aided by constructivist…

  7. Is the σ(600) a glueball? Two photon reactions can tell us

    NASA Astrophysics Data System (ADS)

    Pennington, M. R.

    2001-08-01

    Minkowski and Ochs have recently argued that the small two photon coupling of a conjectured σ(600) is so small that it is likely to be a glueball. We ask whether this can be so or whether it is simply gauge invariance that produces the observed low mass suppression?

  8. Synthesis, antityrosinase activity of curcumin analogues, and crystal structure of (1 E,4 E)-1,5-bis(4-ethoxyphenyl)penta-1,4-dien-3-one

    NASA Astrophysics Data System (ADS)

    Chantrapromma, S.; Ruanwas, P.; Boonnak, N.; Chantrapromma, K.; Fun, H.-K.

    2016-12-01

    Five derivatives of curcumin analogue ( R = OCH2CH3 ( 1), R = N(CH3)2 ( 2), R = 2,4,5-OCH3 ( 3), R = 2,4,6-OCH3 ( 4), and R = 3,4,5-OCH3 ( 5)) were synthesized and characterized by 1H NMR, FT-IR and UV-Vis spectroscopy. The synthesized derivatives were screened for antityrosinase activity, and found that 4 and 5 possess such activity. The crystal structure of 1 was determined by single crystal X-ray diffraction: monoclinic, sp. gr. P21/ c, a = 17.5728(15) Å, b = 5.9121(5) Å, c = 19.8269(13) Å, β = 121.155(5)°, Z = 4. The molecule 1 is twisted with the dihedral angle between two phenyl rings being 15.68(10)°. In the crystal packing, the molecules 1 are linked into chains by C-H···π interactions and further stacked by π···π interactions with the centroid-centroid distance of 3.9311(13) Å.

  9. Electron impact cross sections for surrogates of DNA sugar phosphate backbone

    NASA Astrophysics Data System (ADS)

    Bhowmik, Pooja; Joshipura, K. N.; Pandya, Siddharth

    2012-11-01

    Ionization and elastic cross sections by electron impact on H3PO4 and OP(OCH3)3 which are substitutes for the components of DNA phosphate group. We have employed the Complex Scattering Potential-ionization contribution (CSP-ic) formalism to calculate the cross sections in the energy range from ionization threshold to 2000 eV.

  10. Effects of Rho1, a small GTPase on the production of recombinant glycoproteins in Saccharomyces cerevisiae.

    PubMed

    Xu, Sha; Zhang, Ge-Yuan; Zhang, Huijie; Kitajima, Toshihiko; Nakanishi, Hideki; Gao, Xiao-Dong

    2016-10-21

    To humanize yeast N-glycosylation pathways, genes involved in yeast specific hyper-mannosylation must be disrupted followed by the introduction of genes catalyzing the synthesis, transport, and addition of human sugars. However, deletion of these genes, for instance, OCH1, which initiates hyper-mannosylation, could cause severe defects in cell growth, morphogenesis and response to environmental challenges. In this study, overexpression of RHO1, which encodes the Rho1p small GTPase, is confirmed to partially recover the growth defect of Saccharomyces cerevisiae Δalg3Δoch1 double mutant strain. In addition, transmission electron micrographs indicated that the cell wall structure of RHO1-expressed cells have an enhanced glucan layer and also a recovered mannoprotein layer, revealing the effect of Rho1p GTPase on cell wall biosynthesis. Similar complementation phenotypes have been confirmed by overexpression of the gene that encodes Fks2 protein, a catalytic subunit of a 1,3-β-glucan synthase. Besides the recovery of cell wall structure, the RHO1-overexpressed Δalg3Δoch1 strain also showed improved abilities in temperature tolerance, osmotic potential and drug sensitivity, which were not observed in the Δalg3Δoch1-FKS2 cells. Moreover, RHO1 overexpression could also increase N-glycan site occupancy and the amount of secreted glycoproteins. Overexpression of RHO1 in 'humanized' glycoprotein producing yeasts could significantly facilitate its future industrial applications for the production of therapeutic glycoproteins.

  11. The Brief Child and Family Phone Interview (BCFPI): 1. Rationale, Development, and Description of a Computerized Children's Mental Health Intake and Outcome Assessment Tool

    ERIC Educational Resources Information Center

    Cunningham, Charles E.; Boyle, Michael H.; Hong, Sunjin; Pettingill, Peter; Bohaychuk, Donna

    2009-01-01

    Background: This study describes the development of the Brief Child and Family Phone Interview (BCFPI)--a computer-assisted telephone interview which adapts the revised Ontario Child Health Study's (OCHS-R) parent, teacher, and youth self-report scales for administration as intake screening and treatment outcome measures in children's mental…

  12. Polymerizable 2(2-hydroxynaphthyl)2H-benzotriazole compounds

    DOEpatents

    Gomez, Peter M.; Neidlinger, Hermann H.

    1991-01-01

    Benzotriazole compounds having the formula: ##STR1## wherein R.sub.1 is H, Cl, or OCH.sub.3 ; R.sub.2 is a hydroxynaphthyl group; and R.sub.3 is a vinyl unsaturated polymerizable group. Homopolymers or copolymers thereof are effective as UV light stabilizers and absorbers.

  13. Polymerizable 2(2-hydroxynaphthyl)2H-benzotriazole compounds

    DOEpatents

    Gomez, P.M.; Neidlinger, H.H.

    1991-07-16

    Benzotriazole compounds having the formula: ##STR1## wherein R.sub.1 is H, Cl, or OCH.sub.3 ; R.sub.2 is a hydroxynaphthyl group; and R.sub.3 is a vinyl unsaturated polymerizable group. Homopolymers or copolymers thereof are effective as UV light stabilizers and absorbers.

  14. Thermodynamic Properties of Carbosilane Dendrimers of the Sixth Generation with Ethylene Oxide Terminal Groups.

    PubMed

    Sologubov, Semen S; Markin, Alexey V; Smirnova, Natalia N; Novozhilova, Natalia A; Tatarinova, Elena A; Muzafarov, Aziz M

    2015-11-12

    The temperature dependences of heat capacities of carbosilane dendrimers of the sixth generation with ethyleneoxide terminal groups, denoted as G6[(OCH2CH2)1OCH3]256 and G6[(OCH2CH2)3OCH3]256, were measured in the temperature range from T = (6 to 520) K by precision adiabatic calorimetry and differential scanning calorimetry (DSC). In the above temperature range the physical transformations, such as glass transition and high-temperature relaxation transition, were detected. The standard thermodynamic characteristics of the revealed transformations were determined and analyzed. The standard thermodynamic functions, namely, heat capacity Cp°(T), enthalpy H°(T) - H°(0), entropy S°(T) - S°(0), and Gibbs energy G°(T) - H°(0) for the range from T → 0 to 520 K, and the standard entropies of formation ΔfS° of the investigated dendrimers in the devitrified state at T = 298.15 K, were calculated per corresponding moles of the notional structural units. The standard thermodynamic properties of dendrimers under study were discussed and compared with literature data for carbosilane dendrimers with different functional terminal groups.

  15. A Voyage through the Radio Universe

    ERIC Educational Resources Information Center

    Spuck, Timothy

    2004-01-01

    Each year, professionals and amateurs alike make significant contributions to the field of astronomy. High school students can also conduct astronomy research. Since 1992, the Radio Astronomy Research Team from Oil City Area Senior High School (OCHS) in Oil City, Pennsylvania, has traveled each year to the National Radio Astronomy Observatory…

  16. 1,2-Diphenylethylamines as potential non-stimulant anorectics.

    PubMed

    Ghosh, P; Bolt, A G; Mrongovius, R I

    1978-01-01

    A series of 1,2-diphenylethylamines has been synthesized in which the phenyl rings were substituted with Cl, OCH3 or CF3 at various positions and in various combinations. Four N-ethylpiperazino and N-ethylmorpholino compounds were also prepared. When tested in rats, some of the compounds were found to be potent anorectics and none of them stimulated motor activity.

  17. Escalation of Agitative Rhetoric: A Case Study of Mattachine Midwest, 1967-1970.

    ERIC Educational Resources Information Center

    Darsey, James

    This paper examines the adequacy of Bowers and Ochs' theory of social movements as applied to the escalating agitative strategies of a dissident group, the homosexual-rights organization Mattachine Midwest. The group's activities are described chronologically, in terms of the strategies employed: petition, promulgation, polarization,…

  18. Peer Socialization into Gendered L2 Mandarin Practices in a Study Abroad Context: Talk in the Dorm

    ERIC Educational Resources Information Center

    Diao, Wenhao

    2016-01-01

    This article reports on the peer socialization of gendered Mandarin practices between three American students and their Chinese roommates in a college dorm in China. Gender is often perceived to be a salient identity category among adult L2 learners overseas. Drawing on the language socialization framework (Ochs and Schieffelin 1984), this study…

  19. Parental Expectations of the Swedish Municipal School of Arts

    ERIC Educational Resources Information Center

    Lilliedahl, Jonathan; Georgii-Hemming, Eva

    2009-01-01

    This article draws on a study designed to analyse parental expectations of the Swedish municipal school of arts (hereafter MSA) (in Swedish: kommunal musik- och kulturskola). The study is based on in-depth interviews conducted and informed by grounded theory. Although parental expectations are scarcely uniform, the study reveals a hope that the…

  20. The Brief Child and Family Phone Interview (BCFPI): 1. Rationale, Development, and Description of a Computerized Children's Mental Health Intake and Outcome Assessment Tool

    ERIC Educational Resources Information Center

    Cunningham, Charles E.; Boyle, Michael H.; Hong, Sunjin; Pettingill, Peter; Bohaychuk, Donna

    2009-01-01

    Background: This study describes the development of the Brief Child and Family Phone Interview (BCFPI)--a computer-assisted telephone interview which adapts the revised Ontario Child Health Study's (OCHS-R) parent, teacher, and youth self-report scales for administration as intake screening and treatment outcome measures in children's mental…

  1. The Oscillating Jet Flap

    DTIC Science & Technology

    1976-03-05

    Borsting Superintendent Provost Reproduction of all or part of this report is authorized This report was prepared by: TTNH A^Tn-F.n SECURITY...Aerospace Laboratory, NLR, Amsterdam. 4. Carleman, T. (1922) "Sur la resolution de certaines equations integrales " Arkiv For Matematik, Astronomi Och Fysik

  2. Adolescent Tobacco and Cannabis Use: Young Adult Outcomes from the Ontario Child Health Study

    ERIC Educational Resources Information Center

    Georgiades, Katholiki; Boyle, Michael H.

    2007-01-01

    Background: This study examines the longitudinal associations between adolescent tobacco and cannabis use and young adult functioning. Methods: Data for analysis come from the Ontario Child Health Study (OCHS), a prospective study of child health, psychiatric disorder and adolescent substance use in a general population sample that began in 1983,…

  3. A Scientist or Salesman? Identity Construction through Referent Honorifics on a Japanese Shopping Channel Program

    ERIC Educational Resources Information Center

    Cook, Haruko Minegishi

    2013-01-01

    This paper explores how referent honorifics contribute to identity construction on a Japanese TV shopping channel program. Drawing on Ochs' twostep model of indexicality (1993, 1996) and Agah's proposal (1993) that honorifics are not directly linked to social status but index a "relative position within events of discursive interaction"…

  4. Co-Construction in Korean Interaction

    ERIC Educational Resources Information Center

    Ju, Hee

    2011-01-01

    This dissertation explores co-construction of a situated activity in a current unit by mainly focusing on hearers' actions. The "co-construction" involves a process of interaction in which speakers and hearers jointly construct the form and the meaning of ongoing utterances even when they disagree with each other (Jacoby & Ochs,…

  5. A Scientist or Salesman? Identity Construction through Referent Honorifics on a Japanese Shopping Channel Program

    ERIC Educational Resources Information Center

    Cook, Haruko Minegishi

    2013-01-01

    This paper explores how referent honorifics contribute to identity construction on a Japanese TV shopping channel program. Drawing on Ochs' twostep model of indexicality (1993, 1996) and Agah's proposal (1993) that honorifics are not directly linked to social status but index a "relative position within events of discursive interaction"…

  6. Role of Protein Glycosylation in Candida parapsilosis Cell Wall Integrity and Host Interaction

    PubMed Central

    Pérez-García, Luis A.; Csonka, Katalin; Flores-Carreón, Arturo; Estrada-Mata, Eine; Mellado-Mojica, Erika; Németh, Tibor; López-Ramírez, Luz A.; Toth, Renata; López, Mercedes G.; Vizler, Csaba; Marton, Annamaria; Tóth, Adél; Nosanchuk, Joshua D.; Gácser, Attila; Mora-Montes, Héctor M.

    2016-01-01

    Candida parapsilosis is an important, emerging opportunistic fungal pathogen. Highly mannosylated fungal cell wall proteins are initial contact points with host immune systems. In Candida albicans, Och1 is a Golgi α1,6-mannosyltransferase that plays a key role in the elaboration of the N-linked mannan outer chain. Here, we disrupted C. parapsilosis OCH1 to gain insights into the contribution of N-linked mannosylation to cell fitness and to interactions with immune cells. Loss of Och1 in C. parapsilosis resulted in cellular aggregation, failure of morphogenesis, enhanced susceptibility to cell wall perturbing agents and defects in wall composition. We removed the cell wall O-linked mannans by β-elimination, and assessed the relevance of mannans during interaction with human monocytes. Results indicated that O-linked mannans are important for IL-1β stimulation in a dectin-1 and TLR4-dependent pathway; whereas both, N- and O-linked mannans are equally important ligands for TNFα and IL-6 stimulation, but neither is involved in IL-10 production. Furthermore, mice infected with C. parapsilosis och1Δ null mutant cells had significantly lower fungal burdens compared to wild-type (WT)-challenged counterparts. Therefore, our data are the first to demonstrate that C. parapsilosis N- and O-linked mannans have different roles in host interactions than those reported for C. albicans. PMID:27014229

  7. Cyclo- and carbophosphazene-supported ligands for the assembly of heterometallic (Cu2+/Ca2+, Cu2+/Dy3+, Cu2+/Tb3+) complexes: synthesis, structure, and magnetism.

    PubMed

    Chandrasekhar, Vadapalli; Senapati, Tapas; Dey, Atanu; Das, Sourav; Kalisz, Marguerite; Clérac, Rodolphe

    2012-02-20

    The carbophosphazene and cyclophosphazene hydrazides, [{NC(N(CH(3))(2))}(2){NP{N(CH(3))NH(2)}(2)}] (1) and [N(3)P(3)(O(2)C(12)H(8))(2){N(CH(3))NH(2)}(2)] were condensed with o-vanillin to afford the multisite coordination ligands [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-OH)(m-OCH(3))}(2)}] (2) and [{N(2)P(2)(O(2)C(12)H(8))(2)}{NP{N(CH(3))N═CH-C (6)H(3)-(o-OH)(m-OCH(3))}(2)}] (3), respectively. These ligands were used for the preparation of heterometallic complexes [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuCa(NO(3))(2)}] (4), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{Cu(2)Ca(2)(NO(3))(4)}]·4H(2)O (5), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(4)}]·CH(3)COCH(3) (6), [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(3)}] (7), and [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuTb(NO(3))(3)}] (8). The molecular structures of these compounds reveals that the ligands 2 and 3 possess dual coordination pockets which are used to specifically bind the transition metal ion and the alkaline earth/lanthanide metal ion; the Cu(2+)/Ca(2+), Cu(2+)/Tb(3+), and Cu(2+)/Dy(3+) pairs in these compounds are brought together by phenoxide and methoxy oxygen atoms. While 4, 6, 7, and 8 are dinuclear complexes, 5 is a tetranuclear complex. Detailed magnetic properties on 6-8 reveal that these compounds show weak couplings between the magnetic centers and magnetic anisotropy. However, the ac susceptibility experiments did not reveal any out of phase signal suggesting that in these compounds slow relaxation of magnetization is absent above 1.8 K.

  8. Involvement of T-cell immunoregulation by ochnaflavone in therapeutic effect on fungal arthritis due to Candida albicans.

    PubMed

    Lee, Jue-Hee

    2011-07-01

    Arthritis due to pathogenic fungi is a serious disease causing rapid destruction of the joint. In the pathogenesis of arthritis, T lymphocytes are considered to be one of the major immune cells. In present study, we examined the T cell immunoregulatory effect by ochnaflavone (Och), a biflavonoid, on arthritis caused by Candida albicans that is the most commonly associated with fungal arthritis. To examine the effects of ochnaflavonon Candida albicans-caused septic arthritis, an emulsified mixture of C. albicans cell wall and complete Freund's adjuvant (CACW/CFA) was injected into BALB/c mice via hind footpad route on days -3, -2, and -1. On Day 0, Och at 1 or 2 mg/dose/time was intratraperitoneally given to mice with the swollen footpad every other day for 3 times. The footpad-edema was measured for 20 days. Results revealed that Och reduced the edema at all dose levels and furthermore, there was app. 45% reduction of the edema in animals given 2 mg-dose at the peak of septic arthritis (p < 0.05). This anti-arthritic effect was accompanied by the diminishing of the DTH (delayed type hypersensitivity) activity against the CACW and by the provoking of the dominant T helper 2 (Th2) type cytokines production (IL-4 and Il-10), which appeared to result in a suppression of T helper 1 cytokines (IFN-γ and IL-2). Besides the T cell immunoregulatory activity, Och inhibited T cells activation as evidenced by the IL-2 reduction from PMA/ionomycin-stimulated Jurkat cell line and in addition, the compound killed macrophages in a dose-dependent manner (p < 0.05). However, Och caused no hemolysis (p < 0.05). These data implicate that Och, which has anti-arthritic activity based on the Th2 dominance as well as macrophage removal, can be safely administered into the blood circulation for treatment of the arthritis caused by C. albicans. Thus, it can be concluded that Och would be an ideal immunologically evaluated agent for treating of Candida arthritis.

  9. New aromatase inhibitors. Synthesis and biological activity of pyridyl-substituted tetralone derivatives.

    PubMed

    Bayer, H; Batzl, C; Hartmann, R W; Mannschreck, A

    1991-09-01

    The (E)-2-(4-pyridylmethylene)-1-tetralones 1-7 (1, H; 2, 5-OCH3; 3, 6-OCH3; 4, 7-OCH3; 5, 5-OH; 6, 6-OH; 7, 7-OH) were obtained by aldol condensation of the corresponding 1-tetralones with 4-pyridinecarboxaldehyde, and in the case of the OH compounds 5 and 7 subsequent ether cleavage of the OCH3-substituted 2-(4-pyridylmethylene)-1-tetralones. Catalytic hydrogenation of 1-4 gave the 2-(4-pyridylmethyl)-1-tetralones 8-11 (8, H; 9, 5-OCH3; 10, 6-OCH3; 11, 7-OCH3). Subsequent ether cleavage of 9-11 led to the corresponding OH compounds 12-14 (12, 5-OH; 13, 6-OH; 14, 7-OH). The enantiomers of 11 and 12 were separated semipreparatively by HPLC on triacetylcellulose. All compounds (1-14) showed an inhibition of human placental aromatase exhibiting relative potencies from 2.2 to 213 [compounds 6 and (+)-12, respectively; aromatase inhibitory potency of aminoglutethimide (AG) = 1]. The compounds exhibited no or only a weak inhibition of desmolase [cholesterol side chain cleavage enzyme; maximum activity shown by 12, 23% inhibition (25 microM); AG, 53% inhibition (25 microM)]. In vivo, however, the compounds were not superior to AG as far as the reduction of the plasma estradiol concentration and the mammary carcinoma (MC) inhibiting properties are concerned (PMSG-primed SD rats as well as DMBA-induced MC of the SD rat, pre- and postmenopausal experiments, and the transplantable MXT-MC of the BD2F1 mouse). This is due to a fast decrease of the plasma E2 concentration inhibiting effect as could be shown by a kinetic experiment. In addition, select compounds inhibited rat ovarian aromatase much less than human placental aromatase (12, factor of 10). Estrogenic effects as a cause for the poor in vivo activity of the test compounds could be excluded, since they did not show affinity for the estrogen receptor.

  10. Comparative photodynamic therapy study using two phthalocyanine derivatives

    PubMed Central

    YSLAS, EDITH INÉS; MILLA, LAURA NATALIA; ROMANINI, SILVIA; DURANTINI, EDGARDO NÉSTOR; BERTUZZI, MABEL; RIVAROLA, VIVIANA ALICIA

    2010-01-01

    In the present study, a comparative photodynamic therapy (PDT) study was performed using the phthalocyanine derivatives, ZnPc(OCH3)4 and ZnPc(CF3)4, in a mouse tumor model, under identical experimental procedures. We studied the ablation of tumors induced by PDT. The end-point was to compare the photodynamic efficacy of ZnPc(OCH3)4 and ZnPc(CF3)4. ZnPc(OCH3)4 and ZnPc(CF3)4 were administered intraperitoneally at a dose of 0.2 mg/kg body weight. The injections of drugs were carried out in Balb/c mice bearing subcutaneously inoculated LM2 mouse mammary adenocarcinoma. Histological examination and serum biochemical parameters were used to evaluate hepatic and renal toxicity and function. Phototherapeutic studies were achieved employing a light intensity of 210 J/cm2. After PDT, tumoral regression analyses were carried out, and the degree of tumor cell death was measured utilizing the vital stain Evan’s blue. In this pilot study, we revealed that the cytotoxic effect of ZnPc(OCH3)4 after PDT led to a higher success rate compared to ZnPc(CF3)4-PDT when both were intraperitoneally injectioned. Both phthalocynanine derivatives were able to induce ablation in the tumors. In summary, these results demonstrate the feasibility of ZnPc(OCH3)4- or ZnPc(CF3)4-PDT and its potential as a treatment for small tumors. PMID:22993594

  11. Sex Steroids, Sex Hormone-Binding Globulin and Cardiovascular Health in Men and Postmenopausal Women: The Rotterdam Study.

    PubMed

    Jaspers, Loes; Dhana, Klodian; Muka, Taulant; Meun, Cindy; Kiefte-de Jong, Jessica C; Hofman, Albert; Laven, Joop S E; Franco, Oscar H; Kavousi, Maryam

    2016-07-01

    The concept of cardiovascular health was recently introduced. Sex steroids and sex hormone-binding globulin (SHBG) influence different health domains, but no studies assessed their role in cardiovascular health. To assess the association between estradiol (E2), testosterone (T), SHBG, and free androgen index (FAI) with cardiovascular health. Analyses included 1647 men (68.6 y) and 1564 naturally postmenopausal women (69.6 y) with available data on sex steroids and cardiovascular health from the population-based Rotterdam Study. E2, T, SHBG, and FAI. To define cardiovascular health, 7 metrics including 3 health factors (total cholesterol, fasting glucose, and blood pressure) and 4 health behaviors (physical activity, smoking, body mass index, and diet) were adopted. Three category levels of each metric were added up to a total score ranged 0-14. Logistic regression was performed to explore the association between E2, T, SHBG, and FAI and optimal cardiovascular health (OCH) (score of 11-14). OCH was reached by 153 men (9.3%) and 162 women (10.4%). The prevalence of OCH was higher in the lowest tertile of E2 (38.9%), and of T (43.8%), and the highest tertile of SHBG (48.1%) in women, and the highest tertile of T (43.1%) and SHBG (47.1%) in men. After adjustment for confounders, OCH was associated with lower T (odds ratio and 95% confidence interval, 0.69 [0.48-1.00]) and lower FAI (0.43 [0.32-0.57]) and higher levels of SHBG (4.55 [2.99-6.94]) among women and with higher levels of SHBG (2.56 [1.45-4.49]) in men. OCH was associated with sex steroids and with SHBG in both men and women. The complexity and temporality of the interrelation between sex steroids, SHBG, and cardiovascular health requires further investigation.

  12. The anatomical location and laterality of orbital cavernous haemangiomas.

    PubMed

    McNab, Alan A; Selva, Dinesh; Hardy, Thomas G; O'Donnell, Brett

    2014-10-01

    To determine the anatomical location and laterality of orbital cavernous haemangiomas (OCH). Retrospective case series. The records of 104 patients with OCH were analyzed. The anatomical location of each OCH defined by the location of a point at the centre of the lesion, and its laterality. There were 104 patients included in the study. No patient had more than one lesion. Sixteen (15.4%) were located in the anterior third of the orbit, 74 (71.2%) were in the middle third, and 14 (13.5%) in the posterior third. In the middle third, 10 of 74 (13.5%) were extraconal and 64 intraconal (86.5%), with 30 of 64 (46.9%) middle third intraconal lesions lying lateral to the optic nerve. Of 104 lesions, 56 (53.8%) were left sided, showing a trend towards a predilection for the left side (p = 0.065). If data from other published series which included data on laterality is added to our own data and analysed, 270 of 468 (57.7%) OCH occurred in the left orbit (p < 0.005). OCH may occur at almost any location within the orbit. The commonest location is the middle third of the orbit, in the intraconal space lateral to the optic nerve. This may reflect an origin of these lesions from the arterial side of the circulation, as there are more small arteries in the intraconal space lateral to the optic nerve than in other locations. A predilection for the left orbit remains unexplained.

  13. Environmental risk assessment of hydrofluoroethers (HFEs).

    PubMed

    Tsai, Wen-Tien

    2005-03-17

    Hydrofluoroethers (HFEs) are being used as third generation replacements to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and perfluorocarbons (PFCs) because of their nearly zero stratospheric ozone depletion and relatively low global warming potential. HFEs have been developed under commercial uses as cleaning solvents (incl., HFE-7500, C7F15OC2H5; HFE-7200, C4F9OC2H5; HFE-7100, C4F9CH3; HFE-7000, n-C3F7OCH3), blowing agents (incl., HFE-245mc, CF3CF2OCH3; HFC-356mec, CF3CHFCF2OCH3), refrigerants (incl., HFE-143a, CF3OCH3; HFE-134, CHF2OCHF2; HFE-245mc, CF3CF2OCH3), and dry etching agents in semiconductor manufacturing, (incl., HFE-227me, CF3OCHFCF3). From the environmental, ecological, and health points of view, it is important to understand their environmental risks for these HFEs from a diversity of commercial applications and industrial processes. This paper aims to introduce these HFEs with respect to physiochemical properties, commercial uses, and environmental hazards (i.e. global warming, photochemical potential, fire and explosion hazard, and environmental partition). Further, it addresses the updated data on the human toxicity, occupational exposure and potential health risk of commercial HFEs. It is concluded that there are few HFEs that still possess some environmental hazards, including global warming, flammability hazard and adverse effect of exposure. The partition coefficient for these HFEs has been estimated using the group contribution method; the values of logKow for commercial HFEs have been estimated to be below 3.5.

  14. Swedish use and validation of Valpar work samples for patients with musculoskeletal neck and shoulder pain.

    PubMed

    Schult, M L; Söderback, I; Jacobs, K

    1995-01-01

    I studien beskrivs vad e bedömning av arbetskapacitet (BAK) innehåller Vid en bedömning av arbetskapacitet jämförs kraven för att utföra ett specifikt arbete, definierat i "The dictionary of Occupational Titles" (DOT), och patientens förmåga att utföra ett arbote vilket definieras med hjälp av sju variabler. Allmän utbildnings nivä. Speciella yrkesförberedelser. Anlag, Intresseområden, Personlig läggning. Fysiska drav och Miljöpåverkan. En bedömning av arbetskapaciteten kan ske antingen genom att observera patienten under arbete påarbetsplatsen eller under simulerat arbete tex genom att använda Valpar systemets arbetsprover.Vid Rehabiliteringsmedicinska kliniken, Karolinska Sjukhuset har tvä av de standardiserade arbetsprovema använts. VCWS 8 "Simulerad moontering" och VCWS 9 "Simulerade rorelser for hela kroppen" for att förbättra bedömningen av patientens arbetskapacitet. VCWS 8 mäter "en persons förmaga att utföra ett monteringsarbete som kräver repetetiva fysiska manipulationer" och VCWS 9 mäter "en persons formåga att röra på bålen, nacken, armarna, händerna och fingrama när de relaterar till funktionellt utförande av ett arbete". Valideringen av arbetsprovema för Svensk anvandning gjordes på en grupp patienter (n = 97) med muskuloskelettal nack- och skulder smärta som deltog i ett rehabiliteringsprogram. VCWS 9 utfördes av åttiofem patienter och VCWS 9 av sextionic patienter.Medelvärdet for patienterna som slutförde VCWS 8 var 83.1% av industriell standard nivå (mätt enligt MTM-Method-Time-Measurement) där den lä gsta gränsen är 87.5% för ett godkännt utförende. Detta innebär att de "inte moter" kraven för detta specifika arbete. I motsats till detta sä nädde patientema som utförde VCWS 9 ett medelvärde pä 108.6% vilket overstiger kravet (87.5%) för industriell standard. Det oväntade resultatet kan kanske förklaras av att patienternas intresseområden vad gäller arbetsfalt endast sammanfoll med

  15. Unusual room temperature activation of 1,2-dialkoxyalkanes by niobium and tantalum pentachlorides.

    PubMed

    Marchetti, Fabio; Pampaloni, Guido; Zacchini, Stefano

    2008-12-28

    The outcome of the reactions of MCl(5) (M = Nb, 1a; M = Ta, 1b) with 1,2-dialkoxyalkanes [i.e. MeO(CH(2))(2)OMe (dme), EtO(CH(2))(2)OEt, MeOCH(2)CH(Me)OMe, MeO(CH(2))(2)OCH(2)Cl, MeO(CH(2))(2)O(CH(2))(2)OMe (diglyme)] depends strictly on the stoichiometry. In the 1 : 1 molar ratio reactions, single C-O bond cleavage occurs, resulting in formation of alkyl chloride and of the complexes [upper bond 1 start]MCl(4)[O(R)CH(R')CH(2)O][upper bond 1 end] [M = Nb, R = Me, R' = H, 3a; M = Ta, R = Me, R' = H, 3b; M = Nb, R = Et, R' = H, 5; M = Nb, R = R' = Me, 6; M = Nb, R = CH(2)Cl, R' = H, 7; M = Nb, R = (CH(2))(2)O(Me)NbCl(5), R' = H, 8], which have been characterized spectroscopically. Moreover, minor amounts of the oxo-bridged adducts MOCl(3)(dme)MCl(5) (M = Nb, 4a; M = Ta, 4b) have been isolated in the reactions involving dme. On the other hand, compounds react with two (or more) equivalents of dme mainly via a multiple C-O bond cleavage process, affording MOCl(3)(dme) (M = Nb, 2a; M = Ta, 2b), 1,4-dioxane and methyl chloride. The oxychloride compounds MOCl(3) (M = Nb, 11a; M = Ta, 11b) have been efficiently obtained by addition of TiCl(4) to 2. Compound 2a is reduced in high yield to the Nb(III) species NbCl(3)(dme), 12, upon treatment with SnBu(3)H. The oxychloride NbOCl(3)(diglyme), 9, 1,4-dioxane, CH(3)Cl and the hexachloroniobate salt [MeOCH(2)CH(2)OCH(2)CH(2)O(H)Me][NbCl(6)], 10, have been identified as products of the reaction of 1a with two equivalents of diglyme. The 1 : 2 molar ratio reaction of 1a with MeOCH(2)CH(Me)OMe gives 2,5-dimethyl-1,4-dioxane. Compound 1a reacts with two equivalents of EtO(CH(2))(2)OEt or MeO(CH(2))(2)OCH(2)Cl yielding Cl(CH(2))(2)OCH(2)CH(3) or O(CH(2)Cl)(2) and diglyme, respectively, but not dioxane, suggesting that fragmentation pathways different from that found for dme are operating. The X-ray molecular structures of 4a, 4b and 10 have been determined.

  16. New unsymmetric dinuclear Cu(II)Cu(II) complexes and their relevance to copper(II) containing metalloenzymes and DNA cleavage.

    PubMed

    Peralta, Rosely A; Neves, Ademir; Bortoluzzi, Adailton J; Dos Anjos, Ademir; Xavier, Fernando R; Szpoganicz, Bruno; Terenzi, Hernán; de Oliveira, Mauricio C B; Castellano, Eduardo; Friedermann, Geraldo R; Mangrich, Antonio S; Novak, Miguel A

    2006-05-01

    The new homodinuclear complexes, [Cu(2)(II)(HLdtb)(mu-OCH(3))](ClO(4))(2) (1) and [Cu(2)(II)(Ldtb)(mu-OCH(3))](BPh(4)) (2), with the unsymmetrical N(5)O(2) donor ligand (H(2)Ldtb) - {2-[N,N-Bis(2-pyridylmethyl)aminomethyl]-6-[N',N'-(3,5-di-tert-butylbenzyl-2-hydroxy)(2-pyridylmethyl)]aminomethyl}-4-methylphenol have been synthesized and characterized in the solid state by X-ray crystallography. In both cases the structure reveals that the complexes have a common {Cu(II)(mu-phenoxo)(mu-OCH(3))Cu(II)} structural unit. Magnetic susceptibility studies of 1 and 2 reveal J values of -38.3 cm(-1) and -2.02 cm(-1), respectively, and that the degree of antiferromagnetic coupling is strongly dependent on the coordination geometries of the copper centers within the dinuclear {Cu(II)(mu-OCH(3))(mu-phenolate)Cu(II)} structural unit. Solution studies in dichloromethane, using UV-Visible spectroscopy and electrochemistry, indicate that under these experimental conditions the first coordination spheres of the Cu(II) centers are maintained as observed in the solid state structures, and that both forms can be brought into equilibrium ([Cu(2)(HLdtb)(mu-OCH(3))](2+)=[Cu(2)(Ldtb)(mu-OCH(3))](+)+H(+)) by adjusting the pH with Et(3)N (Ldtb(2-) is the deprotonated form of the ligand). On the other hand, potentiometric titration studies of 1 in an ethanol/water mixture (70:30 V/V; I=0.1M KCl) show three titrable protons, indicating the dissociation of the bridging CH(3)O(-) group.The catecholase activity of 1 and 2 in methanol/water buffer (30:1 V/V) demonstrates that the deprotonated form is the active species in the oxidation of 3,5-di-tert-butylcatechol and that the reaction follows Michaelis-Menten behavior with k(cat)=5.33 x 10(-3)s(-1) and K(M)=3.96 x 10(-3)M. Interestingly, 2 can be electrochemically oxidized with E(1/2)=0.27 V vs.Fc(+)/Fc (Fc(+)/Fc is the redox pair ferrocinium/ferrocene), a redox potential which is believed to be related to the formation of a phenoxyl radical

  17. OCO and NCO chelated derivatives of heavier group 15 elements. Study on possibility of cyclization reaction via intramolecular ether bond cleavage.

    PubMed

    Dostál, Libor; Jambor, Roman; Růžička, Aleš; Jirásko, Robert; Holeček, Jaroslav; De Proft, Frank

    2011-09-21

    A set of four pincer ligands, either the OCO type ligands L(1-3) [2,6-(ROCH(2))(2)C(6)H(3)](-), where R = Me (L(1)), mesityl (L(2)), t-Bu (L(3)) or novel NCO ligand [2-(Me(2)NCH(2))-6-(t-BuOCH(2))C(6)H(3)](-) was studied. The reaction of L(4)Li with PCl(3) resulted in isolation of [2-(OCH(2))-6-(Me(2)NCH(2))C(6)H(3)]PCl (1) as a result of intramolecular ether bond cleavage and elimination of t-BuCl. The conversion between the organolithium compounds L(1,2,4)Li and AsCl(3) led to the desired chlorides, i.e. (L(1))(2)AsCl (2), L(2)AsCl(2) (3), L(4)AsCl(2) (5), but an analogous reaction using the L(3)Li compound gave [2-(OCH(2))-6-(t-BuOCH(2))C(6)H(3)]AsCl (4) as a result of intramolecular cyclization. The organoantimony chloride L(3)SbCl(2) was shown to undergo very slow cyclization in CDCl(3) again via elimination of t-BuCl giving [2-(OCH(2))-6-(t-BuOCH(2))C(6)H(3)]SbCl (6) and it was demonstrated that this reaction may be accelerated by preparation of L(3)Sb(Cl)(OTf) (7) with more Lewis acidic central atom. On the contrary, both antimony derivatives of the NCO ligand L(4), not only the chloride L(4)SbCl(2) (8) but also the ionic pair containing highly Lewis acidic cation [L(4)SbCl](+)[CB(11)H(12)](-) (9), are stable without any indication for etheral bond cleavage. The situation is rather similar in the case of organobismuth derivatives of L(4), which allowed isolation of compounds L(4)BiCl(2) (10), L(4)Bi(Cl)(OTf) (11) and [L(4)BiCl](+)[CB(11)H(12)](-) (12). All studied compounds were characterized by the help of (1)H and (13)C NMR spectroscopy, ESI mass spectrometry, elemental analysis and (except 1) by single-crystal X-ray diffraction.

  18. Experimental PDT: studies on new Si-phthalocyanines and Si-naphthalocyanines in Cremophor emulsions

    NASA Astrophysics Data System (ADS)

    Shopova, Maria; Mantareva, Vanya; Woehrle, Dieter; Mueller, Silke

    1996-12-01

    In the present work the following silicon (IV) - phthalocyanines and -naphthalocyanines bearing methoxyethylene glycol or methoxypolyethylene glycol covalently bound at the silicon are investigated: SiPc[OCH2CH2OCH3]2 (SiPc1), SiNc[OCH2CH2OCH3]2 (SiNc), SiPc[(OCH2CH2)nOCH3] with n approximately 115 (SiPc2). The phototherapeutic effect was shown at Lewis lung carcinoma implanted in mice. SiPc2 is monomeric soluble in water whereas the other two compounds aggregated in this solvent. Therefore these compounds were dissolved monomer in in aqueous Cremophor solution before in vivo administration. Laser irradiation was applied 7 days after implantation and 24 h after drug administration at the following wavelength (eta) ext: 672 nm for SiPc1 and SiPc2, 782 nm for SiNc. In all cases a fluence rate of 370 mW/cm2 at fluence of 360 J/cm2 was used. The assessment criteria for the tumor response were the changes in the mean tumor diameter with time, regrowth delay and average survival time (AST). According to the first parameter the most promising result was obtained after treatment with SiPc1. For example the mean tumor diameter increases as follows: SiPc1 less than SiPc2 less than SiNc very much less than control group without photosensitizer. The regrowth delay showed the same trend. however, for AST another dependence was observed. AST was the longest for SiPc2 (26 days) and shortest for SiNc (22 days). Compared to the control group (without sensitizer and irradiation) the AST was 9 days longer after SiPc2 treatment. Comparing SiPc1 and SiPc2 the chain length of the substituents does not influence the phototherapeutic properties. The detected therapeutic results probably are connected with the long wavelength absorption of the photosensitizers. The relatively lower affectivity of SiNc may be due to a lower degree of tumor accumulation as it was observed in our preliminary pharmacokinetic studies. It is also possible that the shorter AST after treatment with SiNc is

  19. FTIR gas-phase kinetic study on the reactions of OH radicals and Cl atoms with unsaturated esters: Methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate

    NASA Astrophysics Data System (ADS)

    Colomer, Juan P.; Blanco, María B.; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

    2013-11-01

    The relative-rate technique has been used to obtain rates coefficients for the reactions of the unsaturated esters methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate with OH radicals and chlorine atoms at (298 ± 2) K in synthetic air at a total pressure of (760 ± 10) Torr. The experiments were performed in an environmental chamber using in situ FTIR detection to monitor the decay of the esters relative to different reference compounds. The following room temperature rate coefficients (in units of cm3 molecule-1 s-1) were obtained: k1(OH + (CH3)2Cdbnd CHC(O)OCH3) = (4.46 ± 1.05) × 10-11, k2(Cl + (CH3)2Cdbnd CHC(O)OCH3) = (2.78 ± 0.46) × 10-10, k3(OH + CH3CHdbnd C(CH3)C(O)OCH2CH3) = (8.32 ± 1.93) × 10-11, k4(Cl + CH3CHdbnd C(CH3)C(O)OCH2CH3) = (2.53 ± 0.35) × 10-10, k5(OH + CH2dbnd CHCH2C(O)OCH3) = (3.16 ± 0.57) × 10-11, k4(Cl + CH2dbnd CHCH2C(O)OCH3) = (2.10 ± 0.35) × 10-10. With the exception of the reaction of Cl with methyl-3,3-dimethyl acrylate (k2), for which one determination exists in the literature, this study is the first kinetic study for these reactions under atmospheric pressure. Reactivity trends are discussed in terms of the effect of the alkyl and ester groups attached to the double bond on the overall rate coefficients towards OH radicals. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetimes of the title reactions.

  20. Associated species in vaporized methanol-formaldehyde solutions

    SciTech Connect

    Silverman, D.C.; Freeman, J.J.

    1983-07-01

    Analysis of vaporized methanolic formaldehyde (50 mol % methanol) by gas chromatography revealed a sum of mole percents of formaldehyde, water, and methanol greater than 100%. This inconsistency was not found with vaporized solutions containing 1 or 10 mol % methanol. Direct evidence for an adduct of methanol and formaldehyde (CH/sub 3/OCH/sub 2/OH) in the vapor phase was found by use of infrared spectroscopy. The spectrum exhibited an absorption at 1140 cm/sup -1/ corresponding to a C-O-C stretch. Reasonable agreement was found between the C-O-C mole percent estimated from infrared spectroscopy, the increased amount of material detected by gas chromatography, and the estimated equilibrium mole percent of the adduct CH/sub 3/OCH/sub 2/OH. These results confirm that in completely vaporized methanolic formaldehyde at 373 to 423 K, one type of adduct predominates. It contains one molecule each of formaldehyde and methanol.

  1. The Synthesis and Characterization of Aromatic Hybrid Anderson–Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions

    PubMed Central

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

    2015-01-01

    Four aromatic hybrid Anderson polyoxomolybdates with Fe3+ or Mn3+ as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, 1H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3[FeMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-FeMo6-bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRIS–R=(HOCH2)3C–R)), (TBA)3[FeMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-FeMo6-cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3[MnMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-MnMo6-bzn), and (TBA)3[MnMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-MnMo6-cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mm) sodium salts Na3[FeMo6O18{(OCH2)3CNHCOC6H5}2] (Na-FeMo6-bzn), Na3[FeMo6O18{(OCH2)3CNHCOC8H7}2] (Na-FeMo6-cin), Na3[MnMo6O18{(OCH2)3CNHCOC6H5}2] (Na-MnMo6-bzn), and Na3[MnMo6O18{(OCH2)3CNHCOC8H7}2] (Na-MnMo6-cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate–polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern–Volmer analysis, which suggested the formation of a 1:1 POM–protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example

  2. The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

    PubMed

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

    2015-12-01

    Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic

  3. New State Records of Mosquitoes for Colorado.

    PubMed

    Rose, Dominic A; Kondratieff, B C; Weissmann, M J

    2015-06-01

    The 1967 treatment of the Mosquitoes of Colorado by Harmston and Lawson and subsequent publications have recorded 46 culicid species from Colorado. As part of a study to create an updated synopsis of the mosquitoes of Colorado, adult trapping at numerous localities was conducted in Colorado during the summers of 2013 and 2014. This review also included an examination of mosquito specimens in various relevant museum collections. Aedes (Ochlerotatus) niphadopsis and Ae. (Och.) spencerii spencerii were collected during the 2013 and 2014 field seasons. Records for Ae. (Och.) canadensis canadensis, Ae. (Stegomyia) aegypti, and Uranotaenia (Pseudoficalbia) anhydor syntheta were obtained from examination of museum specimens. These species constitute new state records for Colorado, with 51 species now known from the state.

  4. A Polyurethane Surface Modifier: Contrasting Amphiphilic and Contraphilic Surfaces Driven by block and random Soft Blocks having Trifluoroethoxymethyl and PEG Side Chains

    PubMed Central

    Zhang, Wei; Fujiwara, Tomoko; Taşkent, Hűmeyra; Zheng, Ying; Brunson, Kennard; Gamble, Lara; Wynne, Kenneth J.

    2013-01-01

    A conventional MDI-BD-PTMO polyurethane was modified using 2 wt.% polyurethanes (U) having copolyoxetane soft blocks with hydrophobic 3F, CF3CH2OCH2- and hydrophilic MEn, CH3O(CH2CH2O)nCH2-, n = 3, 7) side chains. In contrast to neat 3F-co-MEn-U, 2 wt.% 3F-co-MEn-U compositions have physically stable morphologies and wetting behavior. Surface composition (XPS) and amphiphilic or contraphilic wetting are controlled by the 3F-co-MEn polyoxetane soft block architecture and MEn side chain length. Importantly, θrec can be tuned for 2 wt.% 3F-co-MEn-U compositions independent of swelling, which is controlled by the bulk polyurethane. AFM imaging led to a new morphological model whereby fluorous/PEG-hard block nano-aggregates combine to form near surface features culminating in micron scale texturing. PMID:24204100

  5. Method for synthesizing thin film electrodes

    DOEpatents

    Boyle, Timothy J.

    2007-03-13

    A method for making a thin-film electrode, either an anode or a cathode, by preparing a precursor solution using an alkoxide reactant, depositing multiple thin film layers with each layer approximately 500 1000 .ANG. in thickness, and heating the layers to above 600.degree. C. to achieve a material with electrochemical properties suitable for use in a thin film battery. The preparation of the anode precursor solution uses Sn(OCH.sub.2C(CH.sub.3).sub.3).sub.2 dissolved in a solvent in the presence of HO.sub.2CCH.sub.3 and the cathode precursor solution is formed by dissolving a mixture of (Li(OCH.sub.2C(CH.sub.3).sub.3)).sub.8 and Co(O.sub.2CCH.sub.3).H.sub.2O in at least one polar solvent.

  6. Anion Transport in Liposomes Responds to Variations in the Anchor Chains and the Fourth Amino Acid of Heptapeptide Ion Channels

    PubMed Central

    Ferdani, Riccardo; Pajewski, Robert; Djedovič, Natasha; Pajewska, Jolanta; Schlesinger, Paul H.; Gokel, George W.

    2008-01-01

    Seven heptapeptide derivatives have been prepared. The peptide structure is (Gly)3Xxx(Gly)3 in which Xxx stands for a variable amino acid. The amino acid variations include azetidine carboxylic acid, pipecolic acid, meta-aminobenzoic acid, proline, and leucine. All seven compounds have a C-terminal benzyl group. In all cases, the heptapeptide's N-terminus was linked to diglycolic acid and a dialkylamine. In five cases, the N-terminal group was didecylamine and in two cases, N-ethyl-N-decyl. Chloride and carboxyfluorescein release from phospholipid vesicles was studied with the result that C10H21N(C2H5) COCH2OCH2CO-NH-(Gly)3Leu(Gly)3-OCH2Ph was the most active. Hill analysis showed that this compound involves pore formation by four monomer units rather than two, as previously found for other members of this family. PMID:19169373

  7. Saturation of the Large Aperture Scintillometer

    NASA Astrophysics Data System (ADS)

    Kohsiek, W.; Meijninger, W. M. L.; Debruin, H. A. R.; Beyrich, F.

    2006-10-01

    The saturation aspects of a large aperture (0.3 m) scintillometer operating over a 10-km path were investigated. Measurements were made over mainly forested, hilly terrain with typical maximum sensible heat fluxes of 300-400 W m -2, and over flat terrain with mainly grass, and typical maximum heat fluxes of 100-150 W m-2. Scintillometer-based fluxes were compared with eddy-correlation observations. Two different schemes for calculating the reduction of scintillation caused by saturation were applied: one based on the work of Hill and Clifford, the other based on Frehlich and Ochs. Without saturation correction, the scintillation fluxes were lower than the eddy-correlation fluxes; the saturation correction according to Frehlich and Ochs increased the scintillometer fluxes to an unrealistic level. Correcting the fluxes after the theory of the Hill and Clifford gave satisfying results

  8. Synthesis of ketones from biomass-derived feedstock

    NASA Astrophysics Data System (ADS)

    Meng, Qinglei; Hou, Minqiang; Liu, Huizhen; Song, Jinliang; Han, Buxing

    2017-01-01

    Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H2O/CH2Cl2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H2O/CH2Cl2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.

  9. Synthesis and in-vitro antimycobacterial activity of fluoroquinolone derivatives containing a coumarin moiety.

    PubMed

    Guo, Qiang; Liu, Ming-Liang; Feng, Lian-Shun; Lv, Kai; Guan, Yan; Guo, Hui-Yuan; Xiao, Chun-Ling

    2011-12-01

    A series of gatifloxacin, ciprofloxacin, and 8-OCH(3) ciprofloxacin coumarin derivatives with remarkable improvement in lipophilicity as compared to the parent fluoroquinolones was designed, synthesized, and characterized by (1) H-NMR, MS, and HRMS. These derivatives were evaluated for their in-vitro activity against Mycobacterium smegmatis CMCC 93202 and MTB H37Rv ATCC 27294. All of the synthesized compounds were less active than the parent compounds against M. smegmatis CMCC 93202, but the activity of compound 6 was found to be 2-8-fold more potent than ciprofloxacin, 8-OCH(3) ciprofloxacin, moxifloxacin, and rifampin, and comparable to gatifloxacin against MTB H37Rv ATCC 27294. These results indicated that the lipophilicity of the tested compounds is not the sole parameter affecting antimycobacterial activity. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. /sup 127/I NQR spectra of some iodine derivatives of dialkyl ethers

    SciTech Connect

    Feshin, V.P.; Voronkov, M.G.; Romanenko, L.S.; Nikitin, P.A.; Dubinskaya, E.I.; Komarov, V.G.

    1987-12-10

    The authors studied the mutual influence of oxygen and iodine atoms in molecules of iodine-substituted dialkyl ethers in its dependence on the number of carbon atoms separating these atoms. For this the authors determined the /sup 127/I NQR spectra (1/2-3/2 transition) of compounds of this type at 77 K. They /sup 127/I NQR spectra (1/2-3/2 transition) of compounds containing the I-C-OR grouping show that in these molecules the OR group is an electron donor. The electron-donor power of the methoxy group is appreciably higher in ICH/sub 2/OCH/sub 3/ than in ClCH/sub 2/OCH/sub 3/.

  11. Vibrational spectrum and force field of dimethyldimethoxysilane

    SciTech Connect

    Tenisheva, T.F.; Lazarev, A.N.

    1986-01-01

    Experimental data is presented on the spectra of (CH/sub 3/)/sub 2/Si(OCH/sub 3/)/sub 2/ (I), (CH/sub 3/)/sub 2/Si(OCD/sub 3/)/sub 2/ (II), and (CD/sub 3/)/sub 2/Si(OCH/sub 3/)/sub 2/ (III). The results of the determination of the force constants on the basis of the optimization of the solution of the inverse mechanical problem of the theory of molecular vibrations with consideration of all the internal degrees of freedom with the exception of the coordinates corresponding to internal rotations are discussed. Raman spectra of I, II, and III in the liquid phase is shown and the IR spectra of amorphous films of I, II, and III are illustrated.

  12. Increasing the activity and enantioselectivity of lipases by sol-gel immobilization: further advancements of practical interest.

    PubMed

    Tielmann, Patrick; Kierkels, Hans; Zonta, Albin; Ilie, Adriana; Reetz, Manfred T

    2014-06-21

    The entrapment of lipases in hydrophobic silicate matrices formed by sol-gel mediated hydrolysis of RSi(OCH3)3/Si(OCH3)4 as originally reported in 1996 has been improved over the years by a number of modifications. In the production of second-generation sol-gel lipase immobilizates, a variety of additives during the sol-gel process leads to increased activity and enhanced stereoselectivity in esterifying kinetic resolution. Recent advances in this type of lipase immobilization are reviewed here, in addition to new results regarding the sol-gel entrapment of the lipase from Burkholderia cepacia. It constitutes an excellent heterogeneous biocatalyst in the acylating kinetic resolution of two synthetically and industrially important chiral alcohols, rac-sulcatol and rac-trans-2-methoxycyclohexanol. The observation that the catalyst can be used 10 times in recycling experiments without losing its significant activity or enantioselectivity demonstrates the practical viability of the sol-gel approach.

  13. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  14. Synthesis of ketones from biomass-derived feedstock

    PubMed Central

    Meng, Qinglei; Hou, Minqiang; Liu, Huizhen; Song, Jinliang; Han, Buxing

    2017-01-01

    Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H2O/CH2Cl2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H2O/CH2Cl2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass. PMID:28139709

  15. Differentiation of neotropical fish species with statistical analysis of fourier transform infrared photoacoustic spectroscopy data.

    PubMed

    Almeida, Francylaine S; Lima, Sandro M; Andrade, Luis H C; Súarez, Yzel R

    2012-07-01

    Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) was applied to nineteen fish species in Brazil's Upper Paraná River basin to identify differences in the structural composition of their scales. To differentiate the species, a canonical discriminant analysis was used to indicate the most important absorption peaks in the mid-infrared region. Significant differences were found in the chemical composition of scales among the studied fish species, with Wilk's lambda = 5.2 × 10(-6), F((13,18,394)) = 37.57, and P < 0.001, indicating that O-CH(2) wag at 1396 cm(-1) can be used as a biomarker of this species group. The species could be categorized into four groups according to phylogenetic similarity, suggesting that the O-CH(2) 1396 cm(-1) absorbance is related to the biological traits of each species. This procedure can also be used to complement evolutionary studies.

  16. Organotitanium(IV) compounds as catalysts for the polymerization of isocyanates: The polymerization of isocyanates with functionalized side chains

    SciTech Connect

    Patten, T.E.; Novak, B.M. Lawrence Berkeley Lab., CA )

    1993-02-01

    Catalysts of the form CpTiCl[sub 2]X, where X = [minus]OCH[sub 2]CF[sub 3], [minus]N(CH[sub 3])[sub 2], or [minus]CH[sub 3] (2a, 2b, 2c; Cp = [eta][sup 5]-cyclopentadienyl), CP*TiCl[sub 2]OCH[sub 2]CF[sub 3](3; Cp* = [eta][sup 5]-pentamethylcyclopentadienyl), and Cp[sub 2]TiClOCH[sub 2]-CF[sub 3](4) were used to polymerize a variety of isocyanates. Titanium-alkoxide, -amide, and -alkyl bonds were all found to be active in initiating the insertion of isocyanate monomer. An advantageous consequence of the lesser Lewis acidity of 2a-c relative to TiCl[sub 3]OCH[sub 2]CF[sub 3](1) is that the polymerization of highly functionalized monomers is possible using 2a-c and not 1. 2-Isocyanotoethyl methacrylate (2IEM) was polymerized, using 2b, through the isocyanato group to a linear polymer; the resulting properties of this material were found to be quite different from what was reported by Graham et al. 2IEM trimer was synthesized and subsequently cross-linked using a free-radical initiator, and it was found that the properties of this material matched those of the earlier report. The Diels-Alder adduct of 2IEM with cyclopentadiene, 2-((2-isocyanatoethoxy)carbonyl)-2-methylbicyclo[2.2.1]hept-5-ene (2IECMBH) was prepared and also polymerized using 2b. The use of cyclopentadienyltitanium trichloride derivatives also provides a general route through which a wide variety of end groups may be incorporated onto the end of the polyisocyanate chain.

  17. Minimum structure requirement of immunomodulatory glycolipids for predominant Th2 cytokine induction and the discovery of non-linear phytosphingosine analogs.

    PubMed

    Toba, Tetsuya; Murata, Kenji; Nakanishi, Kyoko; Takahashi, Bitoku; Takemoto, Naohiro; Akabane, Minako; Nakatsuka, Takashi; Imajo, Seiichi; Yamamura, Takashi; Miyake, Sachiko; Annoura, Hirokazu

    2007-05-15

    Analogs of immunomodulatory glycolipid OCH (2) were prepared and minimum structure requirement to exhibit equivalent profiles was disclosed. Analogs bearing non-linear hydrocarbon chain in the phytosphingosine moiety (18, 19) were shown for the first time to possess comparable cytokine inducing profile to 2. Molecular modeling of 2/hCD1d complex based on the crystal structure of alpha-GalCer (1)/hCD1d complex is also described.

  18. Hot-hole extraction from quantum dot to molecular adsorbate.

    PubMed

    Singhal, Pallavi; Ghosh, Hirendra N

    2015-03-09

    Ultrafast thermalized and hot-hole-transfer processes have been investigated in CdSe quantum dot (QD)/catechol composite systems in which hole transfer from photoexcited QDs to the catechols is thermodynamically favorable. A series of catechol derivatives were selected with different electron-donating and -withdrawing groups, and the effect of these groups on hole transfer and charge recombination (CR) dynamics has been investigated. The hole-transfer time was determined using the fluorescence upconversion technique and found to be 2-10 ps depending on the molecular structure of the catechol derivatives. The hot-hole-transfer process was followed after monitoring 2S luminescence of CdSe QDs. Interestingly, hot-hole extraction was observed only in the CdSe/3-methoxycatechol (3-OCH3) composite system owing to the higher electron-donating property of the 3-methoxy group. To confirm the extraction of the hot hole and to monitor the CR reaction in CdSe QD/catechol composite systems, ultrafast transient absorption studies have been carried out. Ultrafast transient-absorption studies show that the bleach recovery kinetics of CdSe QD at the 2S excitonic position is much faster in the presence of 3-OCH3. This faster bleach recovery at the 2S position in CdSe/3-OCH3 suggests hot-hole transfer from CdSe QD to 3-OCH3. CR dynamics in CdSe QD/catechol composite systems was followed by monitoring the excitonic bleach at the 1S position and was found to decrease with free energy of the CR reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Controlled assembly and solution observation of a 2.6 nm polyoxometalate 'super' tetrahedron cluster: [KFe12(OH)18(alpha-1,2,3-P2W15O56)4]29-.

    PubMed

    Pradeep, Chullikkattil P; Long, De-Liang; Kögerler, Paul; Cronin, Leroy

    2007-11-07

    A nanoscale FeIII-substituted polyoxotungstate [KFe12(OH)18-(alpha-1,2,3-P2W15O56)4]29- is synthesized starting from the trilacunary {P2W15} Dawson cluster and [Fe3(mu3-O)-(CH2=CHCOO)6(H2O)3]1+ to give a 2.6 nm tetrahedral cluster species and the 16 kDa cluster can be directly observed in solution as revealed by mass spectrometry studies.

  20. Lanthanide tetramethoxyborate complexes isolated from reductive amination of 2,6-diformyl-p-cresol

    SciTech Connect

    Matthews, K.D.; Kahwa, I.A. ); Johnson, M.P.; Mague, J.T.; McPherson, G.L. )

    1993-04-14

    Treatment of a hot methanolic solution of 2,6-diformyl-p-cresol (1 mmol), 3,6-dioxa-1,8-octanediamine (2 mmol), and a lanthanide(III) nitrate (1 mmol) with sodium cyanotrihydroborate (1.5 mmol) unexpectedly yields a mixture of isostructural but totally different compounds, [Ln(B(OCH[sub 3])[sub 4])(NO[sub 3])[sub 2](CH[sub 3]OH)[sub 2

  1. Energetics and Dynamics of the Reactions of O(3P) with Dimethyl Methylphosphonate and Saria

    DTIC Science & Technology

    2009-09-15

    a SN2 -like transition geometry, Figure 3c, the axial O-C-H bond angle is slightly bent more for reaction 4, Figure 3d. The products of reaction 4 are...Energetics and Dynamics of the Reactions of O(3P) with Dimethyl Methylphosphonate and Sarin Patrick F. Conforti and Matthew Braunstein* Spectral...calculations were performed on the reaction systems O(3P) + sarin and O(3P) + dimethyl methylphosphonate (DMMP), a sarin simulant. Transition state

  2. Influence of molybdenum on the accumulation and composition of the water-soluble polysaccharides of Plantago psyllium

    SciTech Connect

    Lichino, I.P.; Gomanova, M.I.; Milenysheva, L.I.; Yakovlev, A.I.

    1986-07-01

    The authors have studied the dynamics of the accumulation of polysaccharides in flaxseed plantain when it is given a foliar top dressing with molybdenum, and also their monosaccaride composition and physicochemical properties. The amounts of galacturonic acid were determined by potentiometric titration. The results of the investigations permit the conclusions that molybdenum somewhat decreases the amounts of total monosaccaride complex and of galacturonic acid while considerably raising the amount of -OCH/sub 3/.

  3. Loss of smell but not taste in adult women with Turner's syndrome and other congenital hypogonadisms.

    PubMed

    Ros, Cristina; Alobid, Isam; Centellas, Silvia; Balasch, Juan; Mullol, Joaquim; Castelo-Branco, Camil

    2012-11-01

    To assess the impact of Turner's syndrome (TS) and other congenital hypogonadisms (OCH) on the sense of smell and taste. An analytical study of three independent cohorts was designed: patients affected by TS, OCH, and a control group of healthy women taking contraception. Gynaecological Endocrinology Unit and Smell Clinic in Rhinology Unit of Hospital Clinic of Barcelona. Thirty TS patients between 20 and 50 years of age receiving hormone replacement treatment (HT) were included as the exposed cohort; fourteen age-matched women with OCH taking HT were recruited; forty-three age-matched healthy controls receiving hormone contraception treatment were selected as the control group. This group was matched with an historical cohort of forty healthy women without contraception, used to validate BAST-24 in Hospital Clinic of Barcelona. Clinical history, presence of nasal symptoms, general physical examination, nasal endoscopy, and Barcelona Smell Test-24 (BAST-24) and gustometry were carried out on all patients. TS physical dysmorphology features, intensity of nasal symptoms and signs of nasal obstruction were collected. BAST-24 test included 24 odours to assess both sensory (detection, memory and forced choice) and sensitivity (intensity, irritability, freshness and pleasantness) odour characteristics, as well as 4 tastes to evaluate taste domains (detection and forced choice). Healthy women taking hormone contraception felt odours with more intensity (p=0.002) and less irritability (p<0.001) than the historical cohort. TS patients showed a significant impairment in smell memory (p<0.005) and forced-choice (p<0.001) compared with controls taking contraception, whereas no differences were found in odour sensitivity. Detection of taste was successful in 100% of patients. When considering only individual tastes, none of them showed statistically significant differences between groups. Patients with TS show the impairment of smell but not of taste, compared to OCH and

  4. Unimolecular thermal decomposition of dimethoxybenzenes

    SciTech Connect

    Robichaud, David J. Mukarakate, Calvin; Nimlos, Mark R.; Scheer, Adam M.; Ormond, Thomas K.; Buckingham, Grant T.; Ellison, G. Barney

    2014-06-21

    The unimolecular thermal decomposition mechanisms of o-, m-, and p-dimethoxybenzene (CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}) have been studied using a high temperature, microtubular (μtubular) SiC reactor with a residence time of 100 μs. Product detection was carried out using single photon ionization (SPI, 10.487 eV) and resonance enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry and matrix infrared absorption spectroscopy from 400 K to 1600 K. The initial pyrolytic step for each isomer is methoxy bond homolysis to eliminate methyl radical. Subsequent thermolysis is unique for each isomer. In the case of o-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3}, intramolecular H-transfer dominates leading to the formation of o-hydroxybenzaldehyde (o-HO-C{sub 6}H{sub 4}-CHO) and phenol (C{sub 6}H{sub 5}OH). Para-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} immediately breaks the second methoxy bond to form p-benzoquinone, which decomposes further to cyclopentadienone (C{sub 5}H{sub 4}=O). Finally, the m-CH{sub 3}O-C{sub 6}H{sub 4}-OCH{sub 3} isomer will predominantly follow a ring-reduction/CO-elimination mechanism to form C{sub 5}H{sub 4}=O. Electronic structure calculations and transition state theory are used to confirm mechanisms and comment on kinetics. Implications for lignin pyrolysis are discussed.

  5. Activation of C-O and C-C bonds and formation of novel HAlOH-ether complexes: an EPR study of the reaction of ground-state Al atoms with methylethyl ether and diethyl ether.

    PubMed

    Brunet, François D; Feola, Julie C; Joly, Helen A

    2012-03-15

    Reaction mixtures, containing Al atoms and methylethyl ether (MEE) or diethyl ether (DEE) in an adamantane matrix, were prepared with the aid of a metal-atom reactor known as a rotating cryostat. The EPR spectra of the resulting products were recorded from 77-260 K, at 10 K intervals. Al atoms were found to insert into methyl-O, ethyl-O, and C-C bonds to form CH(3)AlOCH(2)CH(3), CH(3)OAlCH(2)CH(3), and CH(3)OCH(2)AlCH(3), respectively, in the case of MEE while DEE produced CH(3)CH(2)AlOCH(2)CH(3) and CH(3)AlCH(2)OCH(2)CH(3), respectively. From the intensity of the transition lines attributed to the Al atom C-O insertion products of MEE, insertion into the methyl-O bond is preferred. The Al hyperfine interaction (hfi) extracted from the EPR spectra of the C-O insertion products was greater than that of the C-C insertion products, that is, 5.4% greater for the DEE system and 7% greater for the MEE system. The increase in Al hfi is thought to arise from the increased electron-withdrawing ability of the substituents bonded to Al. Besides HAlOH, resulting from the reaction of Al atoms with adventitious water, novel mixed HAlOH:MEE and HAlOH:DEE complexes were identified with the aid of isotopic studies involving H(2)(17)O and D(2)O. The Al and H hfi of HAlOH were found to decrease upon complex formation. These findings are consistent with the nuclear hfi calculated using a density functional theory (DFT) method with close agreement between theory and experiment occurring at the B3LYP level using a 6-311+G(2df,p) basis set.

  6. Calcium-based Lewis acid catalysts.

    PubMed

    Begouin, Jeanne-Marie; Niggemann, Meike

    2013-06-17

    Recently, Lewis acidic calcium salts bearing weakly coordinating anions such as Ca(NTf₂)₂, Ca(OTf)₂, CaF₂ and Ca[OCH(CF₃)₂]₂ have been discovered as catalysts for the transformation of alcohols, olefins and carbonyl compounds. High stability towards air and moisture, selectivity and high reactivity under mild reaction conditions render these catalysts a sustainable and mild alternative to transition metals, rare-earth metals or strong Brønsted acids.

  7. Modulating PCBM-Acceptor Crystallinity and Organic Solar Cell Performance by Judiciously Designing Small-Molecule Mainchain End-Capping Units.

    PubMed

    Jiang, Bo; Yao, Jiannian; Zhan, Chuanlang

    2016-10-05

    In this article, we report that the bulk-size and electron-donating/electron-accepting nature of moieties, which are end-capping onto small-molecule donor mainchain, not only modulate the donor's absorption, molecular frontier orbitals, and phase ordering, but also effectively tune the PC71BM-acceptor phase crystallinity. Compared to the electron-deficient trifluoromethyl (SM-CF3) units on the diketopyrrolopyrrole (DPP) small molecule mainchain ends, the electron-rich methoxyl (SM-OCH3) units ending on the same mainchain help improve the PC71BM-acceptor phase short-range ordering. As a result, the -OCH3 capping small-molecule displays larger short-circuit current density (Jsc) when blended with PC71BM (10.72 ± 0.22 vs. 16.15 ± 0.53 mA/cm(2)). However, the electron-donating nature of -OCH3 raises the donor HOMO level, which leads to a quite small open-circuit voltage (Voc) (0.624 vs. 0.881 V). Replacement of the -OCH3 with the large and weak electron-donating aromatic carbazolyl (SM-Cz) ones affords the small molecule of SM-Cz. The SM-Cz:PC71BM system affords a high Voc of 0.846 V and a large Jsc of 13.33 ± 0.34 mA/cm(2) after thermal annealing, and hence gives a larger power conversion efficiency (PCE) of 6.26 ± 0.13%, which is among the top values achieved so far from the DPP molecules. Taken together, these results demonstrate that engineering the end-capping units on small-molecule donor mainchain can effectively modulate the organic solar cell performance.

  8. A theoretical investigation on kinetics, mechanism, and thermochemistry of the gas-phase reactions of methyl fluoroacetate with OH radicals and fate of alkoxy radical.

    PubMed

    Mishra, Bhupesh Kumar; Deka, Ramesh Chandra

    2014-09-25

    We theoretically investigated OH-initiated hydrogen abstraction reactions of methyl fluoroacetate (MFA) CH2FC(O)OCH3 at the MPWB1K level of theory in conjunction with the 6-31+G(d,p) basis set. Thermodynamic and kinetic data are computed using the comparatively accurate G2(MP2) method. Two most stable conformers of MFA are identified, and the energy difference between them is found to be only 0.32 kcal mol(-1). Both of them are considered for rate coefficient calculations, and the contribution from each of the conformers is found to be quite significant. We propose an indirect mechanism due to validation of pre- and post-reactive complexes. The rate parameters are determined using canonical transition state theory and energetics at the G2(MP2) level. The temperature dependence of the rate constant can be described by the Arrhenius expressions: k = 8.79 × 10(-13) exp[(-377.27 ± 64)/T] cm(3) molecule(-1) s(-1) over a temperature range of 250-450 K. The ΔfH°298 for CH2FC(O)OCH3, CH2FC(O)OC(•)H2, and C(•)HFC(O)OCH3 are also computed using an isodesmic procedure. The OH-driven atmospheric lifetime of MFA was estimated to be 24 days. A mechanistic study to shed light on the atmospheric degradation and the sole fate for the consumption of CH2FC(O)OCH2O(•) radical has also been reported.

  9. Theoretical spectroscopic characterization at low temperatures of S-methyl thioformate and O-methyl thioformate.

    PubMed

    Senent, M L; Puzzarini, C; Hochlaf, M; Domínguez-Gómez, R; Carvajal, M

    2014-09-14

    Highly correlated ab initio methods are employed to determine spectroscopic properties at low temperatures of two S-analogs of methyl formate: S-methyl thioformate CH3-S-CHO (MSCHO) and O-methyl thioformate CH3-O-CHS (MOCHS). Both species are detectable and they are expected to play an important role in Astrochemistry. Molecular properties are compared with those of the O-analog, methyl formate. Both isomers present two conformers cis and trans. cis-CH3-S-CHO represents the most stable structure lying 4372.2 cm(-1) below cis-CH3-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm(-1)) than for MOCHS (1963.6 cm(-1)). Harmonic and anharmonic fundamentals and the corresponding intensities, as well as the rotational constants for the ground vibrational and first excited torsional states and the centrifugal distortions constants, are provided. Low torsional energy levels have been obtained by solving variationally a two dimensional Hamiltonian expressed in terms of the two torsional degrees of freedom. The corresponding 2D potential energy surfaces have been computed at the CCSD(T)/aug-cc-pVTZ level of theory. The methyl torsional barriers V3(cis) are determined to be 139.7 cm(-1) (CH3-S-CHO) and 670.4 cm(-1) (CH3-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm(-1) for CH3-S-CHO and negligible for CH3-O-CHS.

  10. Multilingual Affordances in a Swedish Preschool: An Action Research Project

    ERIC Educational Resources Information Center

    Ljunggren, Åsa

    2016-01-01

    This article summarizes the work and the main findings of an action research project that was conducted in an early childhood education and care setting in the city of Malmö, Sweden in the autumn of 2013 and spring 2014. Rönnerman's model (Aktionsforskning i praktiken: förskola och skola på vetenskaplig grund [Action research in practice:…

  11. Synthesis of Potential Prophylactic Agents against Cyanide Intoxication

    DTIC Science & Technology

    1993-04-12

    compiles th« synthetic procedures described in reports submitted for quarters 9-12 of this contract. We have also colligated structures of all...tingle example of ihn compound class was submitted for biological evaluation this report period, and the physical properties of this agent (1) are...condensation of propiophenone »ith diethyl oxalate (Eq. II) The physical properties of these compounds are summarized in Table 2. a cr, 3 F 4 OCH3 5 CH3

  12. Chiral Pharmaceutical Intermediaries Obtained by Reduction of 2-Halo-1-(4-substituted phenyl)-ethanones Mediated by Geotrichum candidum CCT 1205 and Rhodotorula glutinis CCT 2182

    PubMed Central

    Fardelone, Lucídio C.; Rodrigues, J. Augusto R.; Moran, Paulo J. S.

    2011-01-01

    Enantioselective reductions of p-R1-C6H4C(O)CH2R2 (R1 = Cl, Br, CH3, OCH3, NO2 and R2 = Br, Cl) mediated by Geotrichum candidum CCT 1205 and Rhodotorula glutinis CCT 2182 afforded the corresponding halohydrins with complementary R and S configurations, respectively, in excellent yield and enantiomeric excesses. The obtained (R)- or (S)-halohydrins are important building blocks in chemical and pharmaceutical industries. PMID:21687613

  13. Utilization of useless pesticides in a plasma reactor

    NASA Astrophysics Data System (ADS)

    Lozhechnik, A. V.; Mossé, A. L.; Savchin, V. V.; Skomorokhov, D. S.; Khvedchin, I. V.

    2011-09-01

    Investigations on destruction of isophene C14H18O7N2 and the butyl ether of 2,4-dichlorophenoxyacetic acid (Cl2C6H3OCH2COOCH2CH(CH3)2) are performed. The plasma treatment of toxic waste is implemented in a plasma reactor with a three-jet mixing chamber. Air is used as the plasma-forming gas.

  14. Gas-phase oxidation of methyl crotonate and ethyl crotonate. kinetic study of their reactions toward OH radicals and Cl atoms.

    PubMed

    Teruel, Mariano A; Benitez-Villalba, Julio; Caballero, Norma; Blanco, María B

    2012-06-21

    Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with methyl crotonate and ethyl crotonate have been determined at 298 K and atmospheric pressure. The decay of the organics was monitored using gas chromatography with flame ionization detection (GC-FID), and the rate constants were determined using the relative rate method with different reference compounds. Room temperature rate coeficcients were found to be (in cm(3) molecule(-1) s(-1)): k(1)(OH + CH(3)CH═CHC(O)OCH(3)) = (4.65 ± 0.65) × 10(-11), k(2)(Cl + CH(3)CH═CHC(O)OCH(3)) = (2.20 ± 0.55) × 10(-10), k(3)(OH + CH(3)CH═CHC(O)OCH(2)CH(3)) = (4.96 ± 0.61) × 10(-11), and k(4)(Cl + CH(3)CH═CHC(O)OCH(2)CH(3)) = (2.52 ± 0.62) × 10(-10) with uncertainties representing ±2σ. This is the first determination of k(1), k(3), and k(4) under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated VOCs and reactivity trends are presented. In addition, a comparison between the experimentally determined k(OH) with k(OH) predicted from k vs E(HOMO) relationships is presented. On the other hand, product identification under atmospheric conditions has been performed for the first time for these unsaturated esters by the GC-MS technique in NO(x)-free conditions. 2-Hydroxypropanal, acetaldehyde, formaldehyde, and formic acid were positively observed as degradation products in agreement with the addition of OH to C2 and C3 of the double bond, followed by decomposition of the 2,3- or 3,2-hydroxyalkoxy radicals formed. Atmospheric lifetimes, based on of the homogeneous sinks of the unsaturated esters studied, are estimated from the kinetic data obtained in the present work.

  15. Synthesis and Characterization of New Phosphazene Polymers.

    DTIC Science & Technology

    1988-01-21

    reaction of a poly( alkyl /arylphosphazene). In this study, one-half of the methyl groups in [Ph(Me)PN]n (chosen for its solubility in THF as opposed to...polymerization reaction ; and (5) the derivative chemistry of the preformed poly( alkyl /arylphosphazenes)., Synthesis of Poly( alkyl /arylphosphazenes) SC A... vessels , these phosphoranimines quantitatively eliminate the silyl ether byproduct, Me3SiOCH2CF 3 , to form the poly( alkyl /arylphosphazenes). The synthesis

  16. Synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes with hydrophilic poly(oxyethylene) substituents.

    PubMed

    Li, Renjie; Ma, Pan; Dong, Shuai; Zhang, Xianyao; Chen, Yanli; Li, Xiyou; Jiang, Jianzhuang

    2007-12-24

    A series of amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic poly(oxyethylene) heads and hydrophobic alkoxy tails {Pc[(OC2H4)2OCH3]8}Eu{Pc[(OC2H4)2OCH3]8}Eu[Pc(OCnH2n + 1)8] (n = 6, 8, 10,12) (1-4) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound {Pc[(OC2H4)2OCH3]8}Eu{Pc[(OC2H4)2OCH3]8} and metal-free 2,3,9,10,16,17,23,24-octakis(alkoxy)phthalocyanine H2Pc(OCnH2n + 1)8 (n = 6, 8, 10,12) in the presence of Eu(acac)3.H2O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene (TCB). These novel sandwich triple-decker complexes have been characterized by a wide range of spectroscopic methods and have been electrochemically studied. With the help of the Langmuir-Blodgett (LB) technique, these typical amphiphilic triple-decker complexes have been fabricated into organic field effect transistors (OFET) with an unusual bottom contact configuration. The devices display good OFET performance with the carrier mobility for holes in the direction parallel to the aromatic phthalocyanine rings, which shows dependence on the length of the hydrophobic alkoxy side chains, decreasing from 0.46 for 1 to 0.014 cm2 V(-1) s(-1) for 4 along with the increase in the carbon number in the hydrophobic alkoxy side chains.

  17. Distribution of Ordinary High Water Mark (OHWM) Indicators and Their Reliability in Identifying the Limits of "Waters of the United States" in Arid Southwestern Channels

    DTIC Science & Technology

    2006-02-01

    prepared by Robert W. Lichvar, David C. Finnegan, Michael P. Ericsson, and Walter Ochs, all of the Remote Sensing /Geographical Information Systems and...generated using a HEC-RAS steady flow simulation for each predetermined flood return interval obtained from the gage data and the FFA. HEC-RAS is...approach to obtaining the hydrologic boundary conditions necessary for modeling each distinct flow event and evaluating OHWM indicator distributions

  18. Cracking cavitands: metal-directed scission of phosphinyl-substituted resorcinarenes.

    PubMed

    Chavagnan, Thierry; Sémeril, David; Matt, Dominique; Harrowfield, Jack; Toupet, Loïc

    2015-04-27

    Resorcinarene-derived tetramethylene cavitands bearing a diphenylphosphino group grafted to their wider rim undergo facile, directed C-O bond breaking upon reaction with transition-metal ions in the presence of nucleophiles. One possible reaction mechanism involves formation of a P,O-chelate complex, which weakens the adjacent O-CH2 bond, leading to the formation of an oxacarbenium intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemistry Within Molecular Clusters

    DTIC Science & Technology

    1990-01-01

    DME )nCH3OCH 2 +). We speculate that this is due to the fragments being consumed by an ion-molecule reaction within the cluster. One likely candidate is...the ion-molecule reaction of the fragment cations with a neutral DME , within the bulk cluster to form a trimethyloxonlum cation intermediate. This...the observed products. We therefore speculate that the DME cluster reactions leading to the same products, should involve the same mechanism found to

  20. Theoretical spectroscopic characterization at low temperatures of S-methyl thioformate and O-methyl thioformate

    SciTech Connect

    Senent, M. L.; Puzzarini, C.; Hochlaf, M.; Domínguez-Gómez, R.; Carvajal, M.

    2014-09-14

    Highly correlated ab initio methods are employed to determine spectroscopic properties at low temperatures of two S-analogs of methyl formate: S-methyl thioformate CH{sub 3}-S-CHO (MSCHO) and O-methyl thioformate CH{sub 3}-O-CHS (MOCHS). Both species are detectable and they are expected to play an important role in Astrochemistry. Molecular properties are compared with those of the O-analog, methyl formate. Both isomers present two conformers cis and trans. cis-CH{sub 3}-S-CHO represents the most stable structure lying 4372.2 cm{sup −1} below cis-CH{sub 3}-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm{sup −1}) than for MOCHS (1963.6 cm{sup −1}). Harmonic and anharmonic fundamentals and the corresponding intensities, as well as the rotational constants for the ground vibrational and first excited torsional states and the centrifugal distortions constants, are provided. Low torsional energy levels have been obtained by solving variationally a two dimensional Hamiltonian expressed in terms of the two torsional degrees of freedom. The corresponding 2D potential energy surfaces have been computed at the CCSD(T)/aug-cc-pVTZ level of theory. The methyl torsional barriers V{sub 3}(cis) are determined to be 139.7 cm{sup −1} (CH{sub 3}-S-CHO) and 670.4 cm{sup −1} (CH{sub 3}-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm{sup −1} for CH{sub 3}-S-CHO and negligible for CH{sub 3}-O-CHS.

  1. Multilingual Affordances in a Swedish Preschool: An Action Research Project

    ERIC Educational Resources Information Center

    Ljunggren, Åsa

    2016-01-01

    This article summarizes the work and the main findings of an action research project that was conducted in an early childhood education and care setting in the city of Malmö, Sweden in the autumn of 2013 and spring 2014. Rönnerman's model (Aktionsforskning i praktiken: förskola och skola på vetenskaplig grund [Action research in practice:…

  2. Intramolecular ipso-arylative cyclization of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts through merged gold/visible light photoredox catalysis.

    PubMed

    Bansode, Avinash H; Shaikh, Samir R; Gonnade, Rajesh G; Patil, Nitin T

    2017-08-10

    A visible-light-promoted merged gold/photoredox catalyzed ipso-arylative cyclization has been reported. For instance, the reaction of aryl-alkynoates and N-arylpropiolamides with aryldiazonium salts in the presence of catalytic amounts of [(4-OCH3)C6H4]3PAuCl and Ru(bpy)3(PF6)2 under irradiation using a 32 W CFL bulb gave arylated spirocarbocycles in moderate to good yields.

  3. Water-soluble carbosilane dendrimers: synthesis biocompatibility and complexation with oligonucleotides; evaluation for medical applications.

    PubMed

    Bermejo, Jesus F; Ortega, Paula; Chonco, Louis; Eritja, Ramon; Samaniego, Rafael; Müllner, Matthias; de Jesus, Ernesto; de la Mata, F Javier; Flores, Juan Carlos; Gomez, Rafael; Muñoz-Fernandez, Angeles

    2007-01-01

    Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications.

  4. Vapor pressure of germanium precursors

    NASA Astrophysics Data System (ADS)

    Pangrác, J.; Fulem, M.; Hulicius, E.; Melichar, K.; Šimeček, T.; Růžička, K.; Morávek, P.; Růžička, V.; Rushworth, S. A.

    2008-11-01

    The vapor pressure of two germanium precursors tetrakis(methoxy)germanium (Ge(OCH 3) 4, CASRN 992-91-6) and tetrakis(ethoxy)germanium (Ge(OC 2H 5) 4, CASRN 14165-55-0) was determined using a static method in the temperature range 259-303 K. The experimental vapor pressure data were fit with the Antoine equation. The mass spectra before and after degassing by vacuum distillation at low temperature are also reported and discussed.

  5. New Record and Updated Checklists of the Mosquitoes of Afghanistan and Iraq

    DTIC Science & Technology

    2008-08-12

    claviger (Meigen). Although Buck et al. (1972), Ward (1972), Danilov (1985a, 1985b) reported Cx. univittatus Theobald from Afghanistan, it actually...refers to Cx. perexiguus Theobald according to Harbach (1988). Danilov (1978) stated that Ae. versicolor (Barraud) “may be expected in the mountain...K Ae.(Och. pulcritarsis (Rondani) D - Ae. (Stegomyia) aegypti (Linnaeus) - Anopheles (Anopheles) algeriensis Theobald A3, D, G, W, X A2, G, P An

  6. Ab initio study of the rotational energy barrier in carbonylylide

    NASA Astrophysics Data System (ADS)

    Jean, Y.; Volatron, F.

    1981-10-01

    The rotational energy barrier in carbonylylide CH 2OCH 2 is studied using RHF CI calculations. Depending on the size of the CI and the basis set (STO-3G and 4-31G), values in the range 13-17 kcal/mol are found. At this level of calculation, the mid-point of the isomerization process can be mainly described by the diradical rather than the zwitterion.

  7. Effects of age and sex on copper absorption, turnover, and status

    SciTech Connect

    Johnson, P.E.; Milne, D.B. )

    1991-03-15

    Healthy, free-living men and women aged 20 to 59 years were studied to determine the effects of age and sex on Cu absorption, biological half-life (BH) and status. Additional women who were taking oral contraceptives (OCH) or estrogens were compared to women the same ages who did not take hormones. After an overnight fast, subjects provided a blood sample and ate breakfast labeled with 2.5 {mu}Ci Cu-67. Total Cu-67 ingested was determined after the meal by counting subjects in a whole-body gamma counter. Whole body retention of Cu-67 was monitored by 10 additional counts during the next 21 days. Cu absorption (%A) was calculated by extrapolation of the linear portion of a semi-log plot of % retention vs time. BH was {minus}1n2/slope. %A was significantly greater in women than men aged 20-50, but was not affected by age. BH was not significantly affected by either age or sex. Plasma Cu, enzymatic ceruloplasmin (Cp), and RID Cp were significantly higher in women than men, but SOD and in vitro Cu-67 uptake by RBCs did not differ. None of the biochemical indices were significantly affected by age, except RID Cp, which increased with age. Plasma Cu, enzymatic Cp, and SOD activity were higher in women aged 20-39 taking OCH than in those not taking OCH, but %A and BH did not differ between the groups. Trends in women 50-59 taking estrogen or not were similar to findings for women with/without OCH. These data suggest that dietary Cu requirements may differ between men and women.

  8. Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O-O Bond Formation Pathways by Different Aggregation Patterns.

    PubMed

    Yang, Bing; Jiang, Xin; Guo, Qing; Lei, Tao; Zhang, Li-Ping; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

    2016-05-17

    The oxidation of water to molecular oxygen is the key step to realize water splitting from both biological and chemical perspective. In an effort to understand how water oxidation occurs on a molecular level, a large number of molecular catalysts have been synthesized to find an easy access to higher oxidation states as well as their capacity to make O-O bond. However, most of them function in a mixture of organic solvent and water and the O-O bond formation pathway is still a subject of intense debate. Herein, we design the first amphiphilic Ru-bda (H2 bda=2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru(II) (bda)(4-OTEG-pyridine)2 ] (1, OTEG=OCH2 CH2 OCH2 CH2 OCH3 ) and [Ru(II) (bda)(PySO3 Na)2 ] (2, PySO3 (-) =pyridine-3-sulfonate), which possess good solubility in water. Dynamic light scattering (DLS), scanning electron microscope (SEM), critical aggregation concentration (CAC) experiments and product analysis demonstrate that they enable to self-assemble in water and form the O-O bond through different routes even though they have the same bda(2-) backbone. This work illustrates for the first time that the O-O bond formation pathway can be regulated by the interaction of ancillary ligands at supramolecular level.

  9. Hydrogen production for fuel cells through methane reforming at low temperatures

    NASA Astrophysics Data System (ADS)

    Liu, Zhong-Wen; Jun, Ki-Won; Roh, Hyun-Seog; Park, Sang-Eon

    Hydrogen production for fuel cells through methane (CH 4) reforming at low temperatures has been investigated both thermodynamically and experimentally. From the thermodynamic equilibrium analysis, it is concluded that steam reforming of CH 4 (SRM) at low pressure and a high steam-to-CH 4 ratio can be achieved without significant loss of hydrogen yield at a low temperature such as 550 °C. A scheme for the production of hydrogen for fuel cells at low temperatures by burning the unconverted CH 4 to supply the heat for SRM is proposed and the calculated value of the heat-balanced temperature is 548 °C. SRM with and/or without the presence of oxygen at low temperatures is experimentally investigated over a Ni/Ce-ZrO 2/θ-Al 2O 3 catalyst. The catalyst shows high activity and stability towards SRM at temperatures from 400 to 650 °C. The effects of O 2:CH 4 and H 2O:CH 4 ratios on the conversion of CH 4, the hydrogen yield, the selectivity for carbon monoxide, and the H 2:CO ratio are investigated at 650 °C with a constant CH 4 space velocity. Results indicate that CH 4 conversion increases significantly with increasing O 2:CH 4 or H 2O:CH 4 ratio, and the hydrogen content in dry tail gas increases with the H 2O:CH 4 ratio.

  10. Substituent effects on hydrogen bonding of aromatic amide-carboxylate

    NASA Astrophysics Data System (ADS)

    Sen, Ibrahim; Kara, Hulya; Azizoglu, Akın

    2016-10-01

    N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order to understand the variations in their molecular geometries with respect to the substituents by using 1H NMR, 13C NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in a centrosymmetric R22(8) ring motifs for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two crystallographically independent molecules in BAA-OCH3. DFT computations show that the interaction energies between monomer and dimer are in the range of 0.5-3.8 kcal/mol with the B3LYP/6-31 + G*, B3LYP/6-31 ++G*, B3LYP/6-31 ++G**, and B3LYP/AUG-cc-pVDZ levels of theory. The presence of different hydrogen bond patterns is also governed by the substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4 kcal/mol.

  11. Substituent effects on hydrogen bonding of aromatic amide-carboxylate.

    PubMed

    Sen, Ibrahim; Kara, Hulya; Azizoglu, Akın

    2016-10-05

    N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order to understand the variations in their molecular geometries with respect to the substituents by using (1)H NMR, (13)C NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group forms classic OH⋯O hydrogen bonded dimers in a centrosymmetric R2(2)(8) ring motifs for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic OH⋯O hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two crystallographically independent molecules in BAA-OCH3. DFT computations show that the interaction energies between monomer and dimer are in the range of 0.5-3.8kcal/mol with the B3LYP/6-31+G*, B3LYP/6-31++G*, B3LYP/6-31++G**, and B3LYP/AUG-cc-pVDZ levels of theory. The presence of different hydrogen bond patterns is also governed by the substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4kcal/mol.

  12. New ligand design to promote water compatibility of luminescent quantum dots and gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Mei, Bing C.; Susumu, Kimihiro; Medintz, Igor L.; Delehanty, James B.; Mattoussi, Hedi

    2008-02-01

    We report the design and synthesis of new bidentate ligands to promote biocompatibility of luminescent quantum dots (QDs) and gold nanoparticle (Au-NPs) alike. The ligands use commercially available methoxy-terminated hydroxypoly( ethylene glycol) (HO-PEG-OCH3) and thioctic acid (TA) coupled via a stable amide bond to make TA-PEG-OCH3 ligands. Following a simple transformation of the hydroxyl group into an amine group on the methoxy-PEG, the ligand was attached to thioctic acid via DCC coupling. The use of mono-hydroxy-terminated PEG simplifies the reaction and purification steps. Following ring opening of the TA to form DHLA-PEG-OCH3, cap exchange on CdSe-ZnS core-shell QDs provided homogeneous stable dispersions in buffer solutions. Furthermore, using either the newly designed ligand pure, or mixed with amine-functionalized ligands (DHLA-PEG-NH2) allowed tuning of the surface functionalities of the nanoparticles. Gel electrophoresis, absorption and fluorescence experiments confirmed cap exchange, while microinjection in live cells provided additional verification of the potential utility of these hydrophilic QDs in biology. These ligands were also applied to functionalize Au-NPs, with a substantial improvement of their stability under high salt conditions compared to citrate-functionalized dispersions.

  13. Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O.

    PubMed

    Qin, Zhengbo; Cong, Ran; Wu, Xia; Liu, Zhiling; Xie, Hua; Tang, Zichao; Jiang, Ling; Fan, Hongjun

    2013-07-21

    Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au···HR](-) and inserted [HAuR](-) products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR](-) products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au(-) toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au(-)∕Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au(-)∕Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3](-) product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au···HSCH3](-) one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.

  14. Saccharomyces Cerevisiae Hoc1, a Suppressor of Pkc1, Encodes a Putative Glycosyltransferase

    PubMed Central

    Neiman, A. M.; Mhaiskar, V.; Manus, V.; Galibert, F.; Dean, N.

    1997-01-01

    The Saccharomyces cerevisiae gene PKC1 encodes a protein kinase C isozyme that regulates cell wall synthesis. Here we describe the characterization of HOC1, a gene identified by its ability to suppress the cell lysis phenotype of pkc1-371 cells. The HOC1 gene (Homologous to OCH1) is predicted to encode a type II integral membrane protein that strongly resembles Och1p, an α-1,6-mannosyltransferase. Immunofluorescence studies localized Hoc1p to the Golgi apparatus. While overexpression of HOC1 rescued the pkc1-371 temperature-sensitive cell lysis phenotype, disruption of HOC1 lowered the restrictive temperature of the pkc1-371 allele. Disruption of HOC1 also resulted in hypersensitivity to Calcofluor White and hygromycin B, phenotypes characteristic of defects in cell wall integrity and protein glycosylation, respectively. The function of HOC1 appears to be distinct from that of OCH1. Taken together, these results suggest that HOC1 encodes a Golgi-localized putative mannosyltransferase required for the proper construction of the cell wall. PMID:9055074

  15. Mechanisms for glycolipid antigen-driven cytokine polarization by Valpha14i NKT cells.

    PubMed

    Sullivan, Barbara A; Nagarajan, Niranjana A; Wingender, Gerhard; Wang, Jing; Scott, Iain; Tsuji, Moriya; Franck, Richard W; Porcelli, Steven A; Zajonc, Dirk M; Kronenberg, Mitchell

    2010-01-01

    Certain glycolipid Ags for Valpha14i NKT cells can direct the overall cytokine balance of the immune response. Th2-biasing OCH has a lower TCR avidity than the most potent agonist known, alpha-galactosylceramide. Although the CD1d-exposed portions of OCH and alpha-galactosylceramide are identical, structural analysis indicates that there are subtle CD1d conformational differences due to differences in the buried lipid portion of these two Ags, likely accounting for the difference in antigenic potency. Th1-biasing C-glycoside/CD1d has even weaker TCR interactions than OCH/CD1d. Despite this, C-glycoside caused a greater downstream activation of NK cells to produce IFN-gamma, accounting for its promotion of Th1 responses. We found that this difference correlated with the finding that C-glycoside/CD1d complexes survive much longer in vivo. Therefore, we suggest that the pharmacokinetic properties of glycolipids are a major determinant of cytokine skewing, suggesting a pathway for designing therapeutic glycolipids for modulating invariant NKT cell responses.

  16. Infrared matrix isolation study of the thermal and photochemical reactions of ozone with trimethylgallium.

    PubMed

    Sriyarathne, H Dushanee M; Gudmundsdottir, Anna D; Ault, Bruce S

    2015-03-26

    The thermal and photochemical reactions of (CH3)3Ga and O3 have been explored using a combination of matrix isolation, infrared spectroscopy, and theoretical calculations. Experimental data using twin jet deposition and theoretical calculations demonstrate the formation of multiple product species after deposition, annealing to 35 K, and UV irradiation of the matrices. The products were identified as (CH3)2GaOCH3, (CH3)2GaCH2OH, (CH3)(CH3O)Ga(OCH3), (CH3)2GaCHO, and (CH3)Ga(OCH3)(CH2OH). Product identifications were confirmed by annealing and irradiation behavior, (18)O substitution experiments, and high level theoretical calculations. Merged jet deposition led to a number of stable late reaction products, including C2H6, CH3OH, and H2CO. A white solid film was also noted on the walls of the merged (flow reactor) region of the deposition system, likely due to the formation of Ga2O3.

  17. Dual-level direct dynamics studies for the reactions of dimethyl ether with hydrogen atom and methyl radical.

    PubMed

    Wu, Jia-Yan; Liu, Jing-Yao; Li, Ze-Sheng; Huang, Xu-Ri; Sun, Chia-Chung

    2003-04-15

    The dual-level direct dynamics approach is employed to study the dynamics of the CH(3)OCH(3) + H (R1) and CH(3)OCH(3) + CH(3) (R2) reactions. Low-level calculations of the potential energy surface are carried out at the MP2/6-311+G(d,p) level of theory. High-level energetic information is obtained at the QCISD(T) level of theory with the 6-311+G(3df,3pd) basis set. The dynamics calculations are performed using variational transition state theory (VTST) with the interpolated single-point energies (ISPE) method, and small-curvature tunneling (SCT) is included. It is shown that the reaction of CH(3)OCH(3) with H (R1) may proceed much easier and with a lower barrier height than the reaction with CH(3) radical (R2). The calculated rate constants and activation energies are in good agreement with the experimental values. The calculated rate constants are fitted to k(R1) = 1.16 x 10(-19) T(3) exp(-1922/T) and k(R2) = 1.66 x 10(-28) T(5) exp(-3086/T) cm(3) mol(-1) s(-1) over a temperature range 207-2100 K. Furthermore, a small variational effect and large tunneling effect in the lower temperature range are found for the two reactions.

  18. Crystal structures of triazine-3-thione derivatives by reaction with copper and cobalt salts.

    PubMed

    López-Torres, Elena; Mendiola, Maria Antonia; Pastor, César J

    2006-04-03

    The reaction of 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione L1H2OCH3 with copper(II) chloride leads to the formation of an organic molecule L2 containing two triazine rings linked by a new S-S bond. A binuclear copper(II) complex, 1, containing L1 is also isolated. The reaction of L1H2OCH3 with copper(I) chloride yields a hexanuclear cluster of copper(I), 2, in which the copper atoms form a distorted octahedron with the ligand L1 acting as an NS chelate and sulfur bridge, giving to the copper ion a trigonal geometry by one N and two S atoms. In any reaction of the disulfide L2 with metal salts, complexes containing this molecule are isolated. Reactions with copper(I) and copper(II) chloride and nickel(II) and cadmium(II) nitrate produce the S-S bond cleavage, giving complexes containing the triazine L1 behaving as the NS anion, which show spectroscopic characteristics identical with those formed by reaction with L1H2OCH3. However, the reaction with cobalt(II) nitrate gives a low-spin octahedral cobalt(III) complex, in which an asymmetric rupture of the disulfide L2 has been produced, giving an unexpected complex with a new ligand and keeping the S-S bond.

  19. Study of RF-excited Diethylene Glycol Dimethyl Ether Plasmas by Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Algatti, M. A.; Mota, R. P.; Moreira Júnior, P. W. P.; Honda, R. Y.; Kayama, M. E.; Kostov, K. G.

    2012-12-01

    This paper deals with the study of the fragmentation process of diethylene glycol dimethyl ether (CH3O(CH2CH2O)2CH3) (diglyme here in) molecule in low pressure RF excited plasma discharges. The study was carried out using mass spectrometry. The results showed that for a fixed pressure, the increase of the RF power coupled to the plasma chamber from 1 to 35 W produced a plasma environment much more reactive which increases the population of the ionized species like CH2+ (15 amu), C2H4+ (28 amu), CH3O+ (31 amu), C2H4O+ (44 amu), CH3OCH2CH2+ (59 amu) and CH3OCH2CH2O+ (75 amu). This fact may be attributed to the increase of the electronic temperature that makes predominant the occurrence of inelastic processes that promotes molecular fragmentation. For a fixed value of RF power the increase of pressure from 50 mTorr to 100 mTorr produces the decreasing of the above mentioned chemical species due the lower electronic mean free path. These results suggest that if one wants to keep the monomer's functionality within the plasma deposited films resulting from such kind of discharges one must operate in low power conditions.

  20. Polynitroethyl- and fluorodinitroethyl substituted boron esters.

    PubMed

    Klapötke, Thomas M; Krumm, Burkhard; Moll, Richard

    2013-09-02

    The reaction of boron oxide with various nitro-substituted ethanols (2-nitroethanol, 2-fluoro-2,2-dinitroethanol, 2,2,2-trinitroethanol) furnished the corresponding nitroethyl borates B(OCH2CH2NO2)3 (1), B(OCH2CF(NO2)2)3 (2), and B(OCH2C(NO2)3)3 (3). Fluorination of the anion [(NO2)2CCH2OH](-) (4) resulted in 2-fluoro-2,2-dinitroethanol (5), a precursor for 2, and was thoroughly characterized. An interesting condensation was observed with the anion 4 to form the unusual dianion [(NO2)2CCH2C(NO2)2](2-) (6). All compounds were fully characterized by multinuclear NMR spectroscopy, vibrational spectroscopy (IR, Raman), mass spectrometry and elemental analysis. The chemical, physical and energetic properties of 1-3 and 5 are reported, as well as quantum chemical calculations at the CBS-4M level of theory to predict the enthalpies and energies of formation. X-ray diffraction studies were performed, and the crystal structures for compounds 1-6 were determined and discussed thoroughly. The boron esters 1-3 are of interest as possible candidates for smoke-free, green colorants in pyrotechnic applications, and in case of 2 and 3 also as promising high energy oxidizers. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Fluorine in drug design: a case study with fluoroanisoles.

    PubMed

    Xing, Li; Blakemore, David C; Narayanan, Arjun; Unwalla, Ray; Lovering, Frank; Denny, R Aldrin; Zhou, Huanyu; Bunnage, Mark E

    2015-04-01

    Anisole and fluoroanisoles display distinct conformational preferences, as evident from a survey of their crystal structures. In addition to altering the free ligand conformation, various degrees of fluorination have a strong impact on physicochemical and pharmacokinetic properties. Analysis of anisole and fluoroanisole matched molecular pairs in the Pfizer corporate database reveals interesting trends: 1) PhOCF3 increases log D by ~1 log unit over PhOCH3 compounds; 2) PhOCF3 shows lower passive permeability despite its higher lipophilicity; and 3) PhOCF3 does not appreciably improve metabolic stability over PhOCH3 . Emerging from the investigation, difluoroanisole (PhOCF2 H) strikes a better balance of properties with noticeable advantages of log D and transcellular permeability over PhOCF3 . Synthetic assessment illustrates that the routes to access difluoroanisoles are often more straightforward than those for trifluoroanisoles. Whereas replacing PhOCH3 with PhOCF3 is a common tactic to optimize ADME properties, our analysis suggests PhOCF2 H may be a more attractive alternative, and greater exploitation of this motif is recommended.

  2. Vibrational Spectra and Adsorption of Trisiloxane Superspreading Surfactant at Air/Water Interface Studied with Sum Frequency Generation Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Feng, Jun; Wu, Dan; Wen, Jia; Liu, Shi-lin; Wang, Hong-fei

    2008-08-01

    The C-H stretch vibrational spectra of the trisiloxane superspreading surfactant Silwet L-77 ((CH3)3Si-O-Si(CH3)(C3H6)(OCH2CH2)7-8OCH3)-O-Si(CH3)3) at the air/water interface are measured with the surface Sum Frequency Generation Vibrational Spectroscopy (SFG-VS). The spectra are dominated with the features from the -Si-CH3 groups around 2905 cm-1 (symmetric stretch or SS mode) and 2957 cm-1 (mostly the asymmetric stretch or AS mode), and with the weak but apparent contribution from the -O-CH2- groups around 2880 cm-1 (symmetric stretch or SS mode). Comparison of the polarization dependent SFG spectra below and above the critical aggregate or micelle concentration (CAC) indicates that the molecular orientation of the C-H related molecular groups remained unchanged at different surface densities of the Silwet L-77 surfactant. The SFG-VS adsorption isotherm suggested that there was no sign of Silwet L-77 bilayer structure formation at the air/water interface. The Gibbs adsorption free energy of the Silwet surfactant to the air/water interface is -42.2±0.8kcal/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant.

  3. Studies on the relative reactivity of three hydroxyl groups in aconitine.

    PubMed

    She, Xue-Ke; Jian, Xi-Xian; Chen, Dong-Lin; Chen, Qiao-Hong; Wang, Feng-Peng

    2012-01-01

    The relative reactivity of three hydroxyl groups in aconitine toward acetylation, chlorination, sulfonylation, and oxidation has been studied in this paper. The reduction of C-3 ketone and C-15 ketone derivatives of aconitine was also investigated. It was found that (1) the relative reactivity of three hydroxyl groups toward acetylation, chlorination, and sulfonylation is 3-OH>13-OH>15-OH; (2) 3-OH is much more reactive than 15-OH toward oxidation; and (3) reduction of the carbonyl group at C-3 with NaBH(4) generated a pair of C-3 epimers, while the reduction products of the carbonyl group at C-15 depend largely on the specific reducing agent and the absolute configuration of 16-OCH(3). When the substrate has 16β-OCH(3), its carbonyl group at C-15 can be reduced with NaBH(4) to yield exclusively the 15α-OH-containing product. Upon replacement of reducing agent NaBH(4) with LiAlH(4), the C-15 carbonyl group can be reduced to yield a pair of C-15 epimers. On the other hand, when the substrate has 16α-OCH(3), C-15 carbonyl group can only be reduced to generate 15α-OH-containing product.

  4. Comments on the ring-opening polymerization of morpholine-2,5-dione derivatives by various metal catalysts and characterization of the products formed in the reactions involving R2SnX2, where X = OPr(i) and NMe2 and R = Bu(n), Ph and p-Me2NC6H4.

    PubMed

    Chisholm, M H; Galucci, J; Krempner, C; Wiggenhorn, C

    2006-02-14

    (3S,6S)-3-Isopropyl-6-methyl-morpholine-2,5-dione (1), and (3S,6S)-3,6-dimethyl-morpholine-2,5-dione (2), do not enter into ring-opening polymerization reactions with metal catalyst precursors commonly employed for lactides, and with Sn(II) octanoate, only low molecular weight oligomers are obtained. Reactions with R2SnX2 compounds, where R = Ph, Bu(n) and p-Me2NC6H4 and X = OPr(i) or NMe2, reveal that ring-opening of the morpholine-2,5-diones does occur, but that polymerization is terminated by the formation of kinetically-inert products such as {Ph2Sn[mu,eta(3)-OCH(Me)CONCH(Pr(i))COOPr(i)]}2 (3), and {[Bu(n))2Sn[mu,eta(3)-OCH(Me)CONCH(Me)CONMe2]}2 (4), with elimination of HX. Ph3SnOPr(i) is seen to react reversibly with morpholine-2,5-diones in toluene-d8 by 1H NMR spectroscopy while (Bu(n))3SnNMe2 reacts by ring opening to give (Bu(n))3SnOCH(Me)C(O)NHCHMeC(O)NMe2. The new organotin compounds have been characterized by 1H, 13C{1H} and 118Sn NMR spectroscopy and compounds 1, 2, 3 and 4 by single crystal X-ray crystallography.

  5. Dimethyl ether chemical ionization of arylalkylamines.

    PubMed

    Ramos, L E; Cardoso, A M; Correia, A J; Nibbering, N M

    2000-01-01

    The gas-phase reactions of dimethyl ether (DME) ions with a number of biologically active arylalkylamines of the general formula R(1)R(2)C(6)H(3)CHR(3)(CH(2))(n)NR(4)R(5), where R(1) = H or OH, R(2) = H, F, NO(2), OH or OCH(3), R(3) = H or OH, R(4) and R(5) = H or CH(3), have been studied by means of chemical ionization mass spectrometry. Under the experimental conditions used, the most abundant DME ion is the methoxymethyl cation (CH(3)OCH(2)(+), m/z 45). The unimolecular metastable decompositions of the [M + 45](+), [M + 13](+) and [M + 15](+) adducts formed have been interpreted in terms of the initial site of reaction with the amines and the presence of different functional groups in the molecule. This has permitted establishment of general fragmentation patterns for the adducts, and their correlation with structural features of the molecules. The main site of reaction of the ion CH(3)OCH(2)(+) with the amines seems to be the amino group, particularly if the amine is primary, although a competition with attack on the aromatic ring and especially on the benzylic hydroxy group is observed. In a few cases the reaction mechanisms have been elucidated through the use of deuterated amines obtained by H/D exchange with D(2)O. Copyright 2000 John Wiley & Sons, Ltd.

  6. Methyl-perfluoroheptene-ethers (CH3OC7F13): measured OH radical reaction rate coefficients for several isomers and enantiomers and their atmospheric lifetimes and global warming potentials.

    PubMed

    Jubb, Aaron M; Gierczak, Tomasz; Baasandorj, Munkhbayar; Waterland, Robert L; Burkholder, James B

    2014-05-06

    Mixtures of methyl-perfluoroheptene-ethers (CH3OC7F13, MPHEs) are currently in use as replacements for perfluorinated alkanes (PFCs) and poly-ether heat transfer fluids, which are persistent greenhouse gases with lifetimes >1000 years. At present, the atmospheric processing and environmental impact from the use of MPHEs is unknown. In this work, rate coefficients at 296 K for the gas-phase reaction of the OH radical with six key isomers (including stereoisomers and enantiomers) of MPHEs used commercially were measured using a relative rate method. Rate coefficients for the six MPHE isomers ranged from ∼ 0.1 to 2.9 × 10(-12) cm(3) molecule(-1) s(-1) with a strong stereoisomer and -OCH3 group position dependence; the (E)-stereoisomers with the -OCH3 group in an α- position relative to the double bond had the greatest reactivity. Rate coefficients measured for the d3-MPHE isomer analogues showed decreased reactivity consistent with a minor contribution of H atom abstraction from the -OCH3 group to the overall reactivity. Estimated atmospheric lifetimes for the MPHE isomers range from days to months. Atmospheric lifetimes, radiative efficiencies, and global warming potentials for these short-lived MPHE isomers were estimated based on the measured OH rate coefficients along with measured and theoretically calculated MPHE infrared absorption spectra. Our results highlight the importance of quantifying the atmospheric impact of individual components in an isomeric mixture.

  7. Origin of Substituent Effect on Tautomeric Behavior of 1,2,4-Triazole Derivatives: Combined Spectroscopic and Theoretical Study.

    PubMed

    Sergeieva, Tetiana; Bilichenko, Maria; Holodnyak, Sergiy; Monaykina, Yulia V; Okovytyy, Sergiy I; Kovalenko, Sergiy I; Voronkov, Eugene; Leszczynski, Jerzy

    2016-12-29

    The reaction of 2-aryl-[1,2,4]triazolo[1,5-c]quinazolines with nucleophilic reagents (hydrazine hydrate, sodium hydroxide, sodium methoxide, hydrochloric acid) under acidic conditions leads to formation of compounds that tend to tautomerize. The products of the transformation are distinguished by the position (ortho-, meta-, para-) of the OCH3 group in the aryl moiety. To assign their structures we used the combined approach: experiment and theoretical modeling. The procedure included calculation of the relative stability for possible tautomers, simulation of UV/vis spectra for the most stable forms, and comparison of the resulting curves with the experimental spectral data taking into account the Boltzmann weighting. Through computations, we showed that the orientation of OCH3 substituent remarkably impacts on the tautomeric behavior of triazoles. In the case of ortho-OCH3 it is controlled by formation of the intramolecular hydrogen bond while for meta- and para- derivatives the degree of conjugation plays the decisive role. In order to balance the accuracy and cost of calculations we evaluated the performance of selected DFT methods and 6-31G*, 6-311++G**, and STO(##)-3Gel basis sets. The last one is a physically justified basis set previously constructed in our group, and its combination with PBE1PBE approach is shown to be the best choice for UV/vis simulations in the frame of the current research.

  8. Structural characterization of a beta-diketone hydrolase from the cyanobacterium Anabaena sp. PCC 7120 in native and product-bound forms, a coenzyme A-independent member of the crotonase suprafamily.

    PubMed

    Bennett, Joseph P; Whittingham, Jean L; Brzozowski, A Marek; Leonard, Philip M; Grogan, Gideon

    2007-01-09

    The gene alr4455 from the well-studied cyanobacterium Anabaena sp. PCC 7120 encodes a crotonase orthologue that displays beta-diketone hydrolase activity. Anabaena beta-diketone hydrolase (ABDH), in common with 6-oxocamphor hydrolase (OCH) from Rhodococcus sp. NCIMB 9784, catalyzes the desymmetrization of bicyclo[2.2.2]octane-2,6-dione to yield [(S)-3-oxocyclohexyl]acetic acid, a reaction unusual among the crotonase superfamily as the substrate is not an acyl-CoA thioester. The structure of ABDH has been determined to a resolution of 1.5 A in both native and ligand-bound forms. ABDH forms a hexamer similar to OCH and features one active site per enzyme monomer. The arrangement of side chains in the active site indicates that while the catalytic chemistry may be conserved in OCH orthologues, the structural determinants of substrate specificity are different. In the active site of ligand-bound forms that had been cocrystallized with the bicyclic diketone substrate bicyclo[2.2.2]octane-2,6-dione was found the product of the asymmetric enzymatic retro-Claisen reaction [(S)-3-oxocyclohexyl]acetic acid. The structures of ABDH in both native and ligand-bound forms reveal further details about structural variation and modes of coenzyme A-independent activity within the crotonases and provide further evidence of a wider suprafamily of enzymes that have recruited the crotonase fold for the catalysis of reactions other than those regularly attributed to canonical superfamily members.

  9. Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O

    NASA Astrophysics Data System (ADS)

    Qin, Zhengbo; Cong, Ran; Wu, Xia; Liu, Zhiling; Xie, Hua; Tang, Zichao; Jiang, Ling; Fan, Hongjun

    2013-07-01

    Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au⋯HR]- and inserted [HAuR]- products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR]- products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au- toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au-/Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au-/Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3]- product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au⋯HSCH3]- one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.

  10. Reactivity of a rhenium hydroxo-carbonyl complex toward carbon disulfide: insights from theory.

    PubMed

    Yeguas, Violeta; Campomanes, Pablo; López, Ramón

    2010-01-21

    The reaction mechanism on the formation of the hydrosulfido complex [Re(SH)(CO)(3)(bipy)] via the reaction of [Re(OH)(CO)(3)(bipy)] with carbon disulfide was theoretically investigated at the B3LYP/6-31+G(d,p) (LANL2DZ+f for Re) level of theory taking into account bulk solvent effects by using the PCM-UAHF continuum model. The energetics of the process was also analyzed by means of single-point energy calculations by replacing the B3LYP functional by the B3PW91, M05, TPSS and TPSSh ones. The most favored mechanistic routes obtained by us uncover all the molecular rearrangements involved in the reactive process, thus allowing the enriching of the experimental mechanistic proposal. Besides, our findings permit to explain the assignment of the solution color change to the formation of [Re(SH)(CO)(3)(bipy)] when mixed CS(2) with [Re(OH)(CO)(3)(bipy)]. Finally, based on our mechanistic study is also possible to rationalize the formation of [Re(SC(S)OCH(3))(CO)(3)(bipy)] when [Re(OCH(3))(CO)(3)(bipy)] reacts with CS(2) and of TpZn-OCH(3) when methanol is present in the reaction of TpZn-OH with CS(2).

  11. Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH₂CH₃. Isolation of CH₃CH₂OC(O)SH.

    PubMed

    Juncal, Luciana C; Cozzarín, Melina V; Romano, Rosana M

    2015-03-15

    ROC(S)SC(O)OCH2CH3, with R=CH3-, (CH3)2CH- and CH3(CH2)2-, were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by (1)H and (13)C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R=CH3- and (CH3)2CH-, while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the C=S double bond anti (A) with respect to the C-S single bond and the S-C single bond syn (S) with respect to the C=O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(C=O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(C=S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n→π∗ electronic transition associated with the C=S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Molecular cycloencapsulation augments solubility and improves therapeutic index of brominated noscapine in prostate cancer cells

    PubMed Central

    Madan, Jitender; Baruah, Bharat; Nagaraju, Mulpuri; Abdalla, Mohamed O.; Yates, Clayton; Turner, Timothy; Rangari, Vijay; Hamelberg, Donald; Aneja, Ritu

    2012-01-01

    We have previously shown that a novel microtubule-modulating noscapinoid, EM011 (9-Br-Nos), displays potent anticancer activity by inhibition of cellular proliferation and induction of apoptosis in prostate cancer cells and preclinical mice models. However, physicochemical and cellular barriers encumber the development of viable formulations for future clinical translation. To circumvent these limitations, we have synthesized EM011-cyclodextrin inclusion complexes to improve solubility and enhance therapeutic index of EM011. Phase solubility analysis indicated that EM011 formed a 1:1 stoichiometric complex with β-CD and methyl-β-CD, with a stability constant (Kc) of 2.42 × 10−3 M and 4.85 × 10−3 M, respectively. Fourier transform infrared spectroscopy suggested the penetrance of either O-CH2 or OCH3-C6H4-OCH3 moiety of EM011 in the β-CD or methyl-β-CD cavity. In addition, multifarious techniques viz., differential scanning calorimetry, powder X-ray diffraction, scanning electron microscopy, NMR spectroscopy, and computational studies validated the cage complex of EM011 with β-CD and methyl-β-CD. Moreover, rotating frame overhauser enhancement spectroscopy showed that the Ha proton of OCH3-C6H4-OCH3 moiety was in close proximity with H3 proton of β-CD or methyl-β-CD cavity. Furthermore, we found that the solubility of EM011 in phosphate buffer saline (pH 7.4) was enhanced by ∼11 fold and ∼21 fold upon complexation with β-CD and methyl-β-CD, respectively. The enhanced dissolution of the drug CD-complexes in aqueous phase remarkably decreased their IC50 to 28.5 μM (9-Br-Nos-β-CD) and 12.5 μM (9-Br-Nos-methyl-β-CD) in PC-3 cells compared to free EM011 (∼200 μM). This is the first report to demonstrate the novel construction of cylcodextrin-based nanosupramolecular vehicles for enhanced delivery of EM011 that warrants in vivo evaluation for the superior management of prostate cancer. PMID:22540277

  13. Reactions of Monomeric [1,2,4-(Me3C)3C5H2]2CeH and CO with orwithout H2:An Experimental and Computational Study

    SciTech Connect

    Werkema, Evan L.; Maron, Laurent; Eisenstein, Odile; Andersen,Richard A.

    2006-09-07

    Addition of CO to [1,2,4-(Me3C)3C5H2]2CeH, Cp'2CeH, intoluene yields the cis (Cp'2Ce)2(mu-OCHCHO), in which the cis enediolategroup bridges the two metallocene fragments. The cis enediolatequantitatively isomerizes intramolecularly to the trans-enediolate inC6D6 at 100oC over seven months. When the solvent is pentane,Cp'2Ce(OCH2)CeCp'2 forms, in which the oxomethylene group or theformaldehyde dianion bridges the two metallocene fragments. The cisenediolate is suggested to form by insertion of CO into the Ce-C bond ofCp'2Ce(OCH2)CeCp'2 generating Cp'2CeOCH2COCeCp'2. The stereochemistry ofthe cis-enediolate is determined by a 1,2-hydrogen shift in the OCH2COfragment that has the OC(H2) bond anti periplanar relative to the carbenelone pair. The bridging oxomethylene complex reacts with H2, but not withCH4, to give Cp'2CeOMe, which is also the product of the reaction betweenCp'2CeH and a mixture of CO and H2. The oxomethylene complex reacts withCO to give the cis enediolate complex. DFT calculations on C5H5 modelmetallocenes show that the reaction of Cp2CeH with CO and H2 to giveCp2CeOMe is exoergic by 50 kcal mol-1. The net reaction proceeds by aseries of elementary reactions that occur after the formyl complex,Cp2Ce(eta-2 CHO), is formed by further reaction with H2. The key pointthat emerges from the calculated potential energy surface is thebifunctional nature of the metal formyl in which the carbon atom behavesas a donor and acceptor. Replacing H2 by CH4 increases the activationenergy barrier by 17 kcal mol-1.

  14. Evaluating acid and base catalysts in the methylation of milk and rumen fatty acids with special emphasis on conjugated dienes and total trans fatty acids.

    PubMed

    Kramer, J K; Fellner, V; Dugan, M E; Sauer, F D; Mossoba, M M; Yurawecz, M P

    1997-11-01

    Milk analysis is receiving increased attention. Milk contains conjugated octadecadienoic acids (18:2) purported to be anticarcinogenic, low levels of essential fatty acids, and trans fatty acids that increase when essential fatty acids are increased in dairy rations. Milk and rumen fatty acid methyl esters (FAME) were prepared using several acid- (HCl, BF3, acetyl chloride, H2SO4) or base-catalysts (NaOCH3, tetramethylguanidine, diazomethane), or combinations thereof. All acid-catalyzed procedures resulted in decreased cis/trans (delta 9c,11t-18:2) and increased trans/trans (delta 9t,11t-18:2) conjugated dienes and the production of allylic methoxy artifacts. The methoxy artifacts were identified by gas-liquid chromatography (Gl.C)-mass spectroscopy. The base-catalyzed procedures gave no isomerization of conjugated dienes and no methoxy artifacts, but they did not transesterify N-acyl lipids such as sphingomyelin, and NaOCH3 did not methylate free fatty acids. In addition, reaction with tetramethylguanidine coextracted material with hexane that interfered with the determination of the short-chain FAME by GLC. Acid-catalyzed methylation resulted in the loss of about 12% total conjugated dienes, 42% recovery of the delta 9c,11t-18:2 isomer, a fourfold increase in delta 9t,11t-18:2, and the formation of methoxy artifacts, compared with the base-catalyzed reactions. Total milk FAME showed significant infrared (IR) absorption due to conjugated dienes at 985 and 948 cm-1. The IR determination of total trans content of milk FAME was not fully satisfactory because the 966 cm-1 trans band overlapped with the conjugated diene bands. IR accuracy was limited by the fact that the absorptivity of methyl elaidate, used as calibration standard, was different from those of the other minor trans fatty acids (e.g., dienes) found in milk. In addition, acid-catalyzed reactions produced interfering material that absorbed extensively in the trans IR region. No single method or

  15. Molecular cycloencapsulation augments solubility and improves therapeutic index of brominated noscapine in prostate cancer cells.

    PubMed

    Madan, Jitender; Baruah, Bharat; Nagaraju, Mulpuri; Abdalla, Mohamed O; Yates, Clayton; Turner, Timothy; Rangari, Vijay; Hamelberg, Donald; Aneja, Ritu

    2012-05-07

    We have previously shown that a novel microtubule-modulating noscapinoid, EM011 (9-Br-Nos), displays potent anticancer activity by inhibition of cellular proliferation and induction of apoptosis in prostate cancer cells and preclinical mice models. However, physicochemical and cellular barriers encumber the development of viable formulations for future clinical translation. To circumvent these limitations, we have synthesized EM011-cyclodextrin inclusion complexes to improve solubility and enhance therapeutic index of EM011. Phase solubility analysis indicated that EM011 formed a 1:1 stoichiometric complex with β-CD and methyl-β-CD, with a stability constant (K(c)) of 2.42 × 10(-3) M and 4.85 × 10(-3) M, respectively. Fourier transform infrared spectroscopy suggested the penetrance of either a O-CH(2) or OCH(3)-C(6)H(4)-OCH(3) moiety of EM011 in the β-CD or methyl-β-CD cavity. In addition, multifarious techniques, namely, differential scanning calorimetry, powder X-ray diffraction, scanning electron microscopy, NMR spectroscopy, and computational studies validated the cage complex of EM011 with β-CD and methyl-β-CD. Moreover, rotating frame overhauser enhancement spectroscopy showed that the H(a) proton of the OCH(3)-C(6)H(4)-OCH(3) moiety was in close proximity with H3 proton of the β-CD or methyl-β-CD cavity. Furthermore, we found that the solubility of EM011 in phosphate buffer saline (pH 7.4) was enhanced by ~11 fold and ~21 fold upon complexation with β-CD and methyl-β-CD, respectively. The enhanced dissolution of the drug CD-complexes in aqueous phase remarkably decreased their IC(50) to 28.5 μM (9-Br-Nos-β-CD) and 12.5 μM (9-Br-Nos-methyl-β-CD) in PC-3 cells compared to free EM011 (~200 μM). This is the first report to demonstrate the novel construction of cylcodextrin-based nanosupramolecular vehicles for enhanced delivery of EM011 that warrants in vivo evaluation for the superior management of prostate cancer.

  16. Preparation and characterization of nonpolar fluorinated carbosilane dendrimers by APcI mass spectrometry and small-angle X-ray scattering

    SciTech Connect

    Omotowa, B.A.; Keefer, K.D.; Kirchmeier, R.L.; Shreeve, J.M.

    1999-12-08

    The following highly fluorinated nonpolar dendrimers were obtained in high yields from multiple hydrosilylation reactions between core hydride terminated carbosilane dendrimers and allyl-1,1-dihydrotrifluoroethyl ether or allyl-1,1-dihydroheptadecafluorononyl ether through divergent synthetic routes: Si[CH{sub 2}CH{sub 2}SiMe{sub 2}(CH{sub 2}CH{sub 2}CH{sub 2}OCH{sub 2}CF{sub 3})]{sub 4} (7), Si{l{underscore}brace}CH{sub 2}CH{sub 2}SiMe[CH{sub 2}{l{underscore}brace}CH{sub 2}SiMe(CH{sub 2}CH{sub 2}CH{sub 2}OCH{sub 2}CF{sub 3}){sub 2}]{sub 2}{r{underscore}brace}{sub 4} (8), Si[CH{sub 2}CH{sub 2}Si(CH{sub 2}CH{sub 2}CH{sub 2}OCH{sub 2}C{sub 8}F{sub 17}){sub 3}]{sub 4} (9), Si[CH{sub 2}CH{sub 2}SiMe{sub 2}(CH{sub 2}CH{sub 2}OCH{sub 2}C{sub 8}F{sub 17})]{sub 4} (10), and Si{l{underscore}brace}CH{sub 2}CH{sub 2}Si[CH{sub 2}CH{sub 2}Si(CH{sub 2}CH{sub 2}OCH{sub 2}C{sub 8}F{sub 17}){sub 3}]{sub 3}{r{underscore}brace}{sub 4} (11). These compounds were characterized by elemental and spectroscopic analyses. Valuable mass spectral data were obtained by using atmospheric pressure chemical ionization (APcI). The fluorinated dendrimer molecule and the nonfluorinated core scatter X-ray light differently and present unique slopes on the Guinier Plot of data from small-angle X-ray light scattering (SAXS) in hexafluorobenzene. Glass transition temperatures (T{sub g}) and thermogravimetric analyses (TGA) of the dendrimers were determined.

  17. Magnesium Diboride Current Leads

    NASA Technical Reports Server (NTRS)

    Panek, John

    2010-01-01

    A recently discovered superconductor, magnesium diboride (MgB2), can be used to fabricate conducting leads used in cryogenic applications. Dis covered to be superconducting in 2001, MgB2 has the advantage of remaining superconducting at higher temperatures than the previously used material, NbTi. The purpose of these leads is to provide 2 A of electricity to motors located in a 1.3 K environment. The providing environment is a relatively warm 17 K. Requirements for these leads are to survive temperature fluctuations in the 5 K and 11 K heat sinks, and not conduct excessive heat into the 1.3 K environment. Test data showed that each lead in the assembly could conduct 5 A at 4 K, which, when scaled to 17 K, still provided more than the required 2 A. The lead assembly consists of 12 steelclad MgB2 wires, a tensioned Kevlar support, a thermal heat sink interface at 4 K, and base plates. The wires are soldered to heavy copper leads at the 17 K end, and to thin copper-clad NbTi leads at the 1.3 K end. The leads were designed, fabricated, and tested at the Forschungszentrum Karlsruhe - Institut foer Technische Physik before inclusion in Goddard's XRS (X-Ray Spectrometer) instrument onboard the Astro-E2 spacecraft. A key factor is that MgB2 remains superconducting up to 30 K, which means that it does not introduce joule heating as a resistive wire would. Because the required temperature ranges are 1.3-17 K, this provides a large margin of safety. Previous designs lost superconductivity at around 8 K. The disadvantage to MgB2 is that it is a brittle ceramic, and making thin wires from it is challenging. The solution was to encase the leads in thin steel tubes for strength. Previous designs were so brittle as to risk instrument survival. MgB2 leads can be used in any cryogenic application where small currents need to be conducted at below 30 K. Because previous designs would superconduct only at up to 8 K, this new design would be ideal for the 8-30 K range.

  18. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    NASA Astrophysics Data System (ADS)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  19. Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

    PubMed

    Park, J; Lin, M C

    2009-12-03

    The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  20. Formation of ethylene glycol and other complex organic molecules in star-forming regions

    NASA Astrophysics Data System (ADS)

    Rivilla, V. M.; Beltrán, M. T.; Cesaroni, R.; Fontani, F.; Codella, C.; Zhang, Q.

    2017-02-01

    Context. The detection of complex organic molecules related with prebiotic chemistry in star-forming regions allows us to investigate how the basic building blocks of life are formed. Aims: Ethylene glycol (CH2OH)2 is the simplest sugar alcohol and the reduced alcohol of the simplest sugar glycoladehyde (CH2OHCHO). We study the molecular abundance and spatial distribution of (CH2OH)2, CH2OHCHO and other chemically related complex organic species (CH3OCHO, CH3OCH3, and C2H5OH) towards the chemically rich massive star-forming region G31.41+0.31. Methods: We analyzed multiple single-dish (Green Bank Telescope and IRAM 30 m) and interferometric (Submillimeter Array) spectra towards G31.41+0.31, covering a range of frequencies from 45 to 258 GHz. We fitted the observed spectra with a local thermodynamic equilibrium (LTE) synthetic spectra, and obtained excitation temperatures and column densities. We compared our findings in G31.41+0.31 with the results found in other environments, including low- and high-mass star-forming regions, quiescent clouds and comets. Results: We report for the first time the presence of the aGg' conformer of (CH2OH)2 towards G31.41+0.31, detecting more than 30 unblended lines. We also detected multiple transitions of other complex organic molecules such as CH2OHCHO, CH3OCHO, CH3OCH3, and C2H5OH. The high angular resolution images show that the (CH2OH)2 emission is very compact, peaking towards the maximum of the 1.3 mm continuum. These observations suggest that low abundance complex organic molecules, like (CH2OH)2 or CH2OHCHO, are good probes of the gas located closer to the forming stars. Our analysis confirms that (CH2OH)2 is more abundant than CH2OHCHO in G31.41+0.31, as previously observed in other interstellar regions. Comparing different star-forming regions we find evidence of an increase of the (CH2OH)2/CH2OHCHO abundance ratio with the luminosity of the source. The CH3OCH3/CH3OCHO and (CH2OH)2/C2H5OH ratios are nearly constant with

  1. On the structural and electronic considerations concerning the reactivity of metal-metal multiple bonds

    NASA Astrophysics Data System (ADS)

    Glasgow, Katherine Campbell

    2000-10-01

    The previously known compound W2(OCH2tBu) 6(py)2 is crystallographically characterized. Its solid state structure is described and compared with other M2(OR)6L 2 complexes. Upon treatment with isoprene, the complex W2(OCH 2tBu)6(py)(mu-isoprene) forms. The solid state structure is disordered with respect to the orientation of the diene; two different configurations are seen in the crystal structure. These two isomers are in equilibrium in solution and are visible by 1H NMR spectroscopy. Multidimensional NMR experiments are used to assign the structures of the two isomers in solution. Through the use of spin magnetization transfer, it has been determined that the two isomers interconvert through the loss of isoprene. The DeltaH° and DeltaS° values for the equilibrium are determined. The starting material W2(OCH2tBu) 6(py)2 had been previously determined to be an olefin hydrogenation catalyst. It has been determined that cyclic olefins are hydrogenated in a cis manner, and a kinetic isotope effect of 1.7 has been measured. It has been determined that olefins which form isolable adducts with W 2(OCH2tBu)6(py)2, such as isoprene, undergo hydrogenation at approximately the same rate as olefins which do not show evidence of adduct formation. The complex W2(OCH2tBu)6(py) 2had been found to couple aldehydes and ketones stoichiometrically to give olefins. The reaction was found to proceed in a stepwise manner through the alkylidene intermediate W2(OCH2tBu) 6(py)(O)(mu-CHR), allowing the selective cross coupling of aldehydes and ketones. More studies have been undertaken to help determine the scope of the reaction. Competition experiments have been performed to determine reaction preferences. Unsaturated and functionalized aldehydes have been studied to determine the tolerance of the reaction to certain chemical groups. The role of pyridine in this reaction has been studied, especially concerning its reactivity with the alkylidene intermediate. The dimetal tetracarboxylate

  2. High temperature shock tube and theoretical studies on the thermal decomposition of dimethyl carbonate and its bimolecular reactions with H and D-atoms.

    PubMed

    Peukert, S L; Sivaramakrishnan, R; Michael, J V

    2013-05-09

    The shock tube technique was used to study the high temperature thermal decomposition of dimethyl carbonate, CH3OC(O)OCH3 (DMC). The formation of H-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range of 1053-1157 K at pressures ∼0.5 atm. The H-atom profiles were simulated using a detailed chemical kinetic mechanism for DMC thermal decomposition. Simulations indicate that the formation of H-atoms is sensitive to the rate constants for the energetically lowest-lying bond fission channel, CH3OC(O)OCH3 → CH3 + CH3OC(O)O [A], where H-atoms form instantaneously at high temperatures from the sequence of radical β-scissions, CH3OC(O)O → CH3O + CO2 → H + CH2O + CO2. A master equation analysis was performed using CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for all thermal decomposition processes in DMC. The theoretical predictions were found to be in good agreement with the present experimentally derived rate constants for the bond fission channel (A). The theoretically derived rate constants for this important bond-fission process in DMC can be represented by a modified Arrhenius expression at 0.5 atm over the T-range 1000-2000 K as, kA(T) = 6.85 × 10(98)T (-24.239) exp(-65250 K/T) s(-1). The H-atom temporal profiles at long times show only minor sensitivity to the abstraction reaction, H + CH3OC(O)OCH3 → H2 + CH3OC(O)OCH2 [B]. However, H + DMC is an important fuel destruction reaction at high temperatures. Consequently, measurements of D-atom profiles using D-ARAS allowed unambiguous rate constant measurements for the deuterated analog of reaction B, D + CH3OC(O)OCH3 → HD + CH3OC(O)OCH2 [C]. Reaction C is a surrogate for H + DMC since the theoretically predicted kinetic isotope effect at high temperatures (1000 - 2000K) is close to unity, kC ≈ 1.2 kB. TST calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties

  3. Searching for trans ethyl methyl ether in Orion KL★,★★

    PubMed Central

    Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

    2015-01-01

    We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm−2 and ≤(1.0 ± 0.2)× 1015 cm−2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. PMID:26869726

  4. Hydrogen-bonding Interactions between Apigenin and Ethanol/Water: A Theoretical Study

    NASA Astrophysics Data System (ADS)

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui; Lai, Rong-Cai

    2016-10-01

    In this work, hydrogen-bonding interactions between apigenin and water/ethanol were investigated from a theoretical perspective using quantum chemical calculations. Two conformations of apigenin molecule were considered in this work. The following results were found. (1) For apigenin monomer, the molecular structure is non-planar, and all of the hydrogen and oxygen atoms can be hydrogen-bonding sites. (2) Eight and seven optimized geometries are obtained for apigenin (I)–H2O/CH3CH2OH and apigenin (II)–H2O/CH3CH2OH complexes, respectively. In apigenin, excluding the aromatic hydrogen atoms in the phenyl substituent, all other hydrogen atoms and the oxygen atoms form hydrogen-bonds with H2O and CH3CH2OH. (3) In apigenin–H2O/CH3CH2OH complexes, the electron density and the E(2) in the related localized anti-bonding orbital are increased upon hydrogen-bond formation. These are the cause of the elongation and red-shift of the X‑H bond. The sum of the charge change transfers from the hydrogen-bond acceptor to donor. The stronger interaction makes the charge change more intense than in the less stable structures. (4) Most of the hydrogen-bonds in the complexes are electrostatic in nature. However, the C4‑O5···H, C9‑O4···H and C13‑O2···H hydrogen-bonds have some degree of covalent character. Furthermore, the hydroxyl groups of the apigenin molecule are the preferred hydrogen-bonding sites.

  5. Multiheteromacrocycles that Complex Metal Ions. Second Progress Report, 1 May 1975 -- 30 April 1976

    DOE R&D Accomplishments Database

    Cram, D. J.

    1976-01-15

    Objective is to develop cyclic and polycyclic host organic compounds to complex and lipophilize metal ions. Macrorings were synthesized: (OCH{sub 2} CH{sub 2} O CH{sub 2}COCH{sub 2} COCH{sub 2}){sub 2} and (OCH{sub 2} CH{sub 2} O CH{sub 2} COCH{sub 2} COCH{sub 2}){sub 3}. The smaller ring complexes divalent metals 10{sup 1+9} times better than the open-chain model CH{sub 3} O CH{sub 2} CO CH{sub 2} COCH{sub 2} O CH{sub 3}, and the order in which metal ions are complexed is Cu{sup 2+}, UO{sub 2}{sup 2+} greater than Ni{sup 2+} greater than Fe{sup 2+}, Co{sup 2+}, Zn{sup 2+}, Cd{sup 2+} greater than Mn{sup 2+}. The UO{sub 2}{sup 2+} and Cu{sup 2+} complexes were isolated and characterized. The larger ring complexes trivalent metals 10{sup 0.9-1.7} times better than the open- chain model compound, and the order is La{sup 3+}, Ce{sup 3+} greater than Cr{sup 3+}. Five other macrocycles were also synthesized, and their binding constants with Na, K, NH{sub 4}, and Cs picrates were measured. Six compounds containing one macroring and two inward-pointing ArOH or ArOCH{sub 3} groups were also prepared and tested for binding of Li, Na, K, Rb, and NH{sub 4} picrates. Racemic compounds containing two binaphthyls and its sulfur analog were prepared. Cage-shaped multiheteromacrocycles containing ten O ligand sites or four S and six O ligand sites were prepared and the binding capability of the first compound for picrates studied. Two ring systems with phosphonate ester groups were also prepared. (DLC)

  6. Formation of polyhydroxyalkanoate in aerobic anoxygenic phototrophic bacteria and its relationship to carbon source and light availability.

    PubMed

    Xiao, Na; Jiao, Nianzhi

    2011-11-01

    Aerobic anoxygenic phototrophic bacteria (AAPB) are unique players in carbon cycling in the ocean. Cellular carbon storage is an important mechanism regulating the nutrition status of AAPB but is not yet well understood. In this paper, six AAPB species (Dinoroseobacter sp. JL1447, Roseobacter denitrificans OCh 114, Roseobacter litoralis OCh 149, Dinoroseobacter shibae DFL 12(T), Labrenzia alexandrii DFL 11(T), and Erythrobacter longus DSMZ 6997) were examined, and all of them demonstrated the ability to form the carbon polymer polyhydroxyalkanoate (PHA) in the cell. The PHA in Dinoroseobacter sp. JL1447 was identified as poly-beta-hydroxybutyrate (PHB) according to evidence from Fourier transform infrared spectroscopy, differential scanning calorimetry, and (1)H nuclear magnetic resonance spectroscopy examinations. Carbon sources turned out to be critical for PHA production in AAPB. Among the eight media tested with Dinoroseobacter sp. JL1447, sodium acetate, giving a PHA production rate of 72%, was the most productive carbon source, followed by glucose, with a 68% PHA production rate. Such PHA production rates are among the highest recorded for all bacteria. The C/N ratio of substrates was verified by the experiments as another key factor in PHA production. In the case of R. denitrificans OCh 114, PHA was not detected when the organism was cultured at C/N ratios of <2 but became apparent at C/N ratios of >3. Light is also important for the formation of PHA in AAPB. In the case of Dinoroseobacter sp. JL1447, up to a one-quarter increase in PHB production was observed when the culture underwent growth in a light-dark cycle compared to growth completely in the dark.

  7. Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI4(DME)2.

    PubMed

    Travia, Nicholas E; Monreal, Marisa J; Scott, Brian L; Kiplinger, Jaqueline L

    2012-12-28

    The thorium(IV) tetraiodide complex ThI(4)(DME)(2) (3) (DME = 1,2-dimethoxyethane) has been prepared in high yield by reacting the corresponding chloride complex ThCl(4)(DME)(2) with an excess of trimethylsilyl iodide (Me(3)SiI) in toluene. This new route avoids the use of thorium metal as a reagent. ThI(4)(DME)(2) (3) exhibits excellent thermal stability compared to ThI(4)(THF)(4) (1), which undergoes rapid ring-opening of THF at ambient temperature to yield the iodobutoxide complex ThI(3)[O(CH(2))(4)I](THF)(3) (2). Subsequent ligand-exchange between 2 and DME affords ThI(3)[O(CH(2))(4)I](DME)(2) (11), which can be converted to 3 with Me(3)SiI. Salt metathesis between 2 and K(L(Me)) (L(Me) = (2,6-(i)Pr(2)C(6)H(3))NC(Me)CHC(Me)N(2,6-(i)Pr(2)C(6)H(3))) cleanly gives (L(Me))ThI(2)[O(CH(2))(4)I](THF) (10), which is a rare example of a thorium β-diketiminate complex. Complexes 2, 10, and 11 represent the first reported examples of THF ring-opening mediated by thorium. The synthetic utility of ThI(4)(DME)(2) (3) is demonstrated by preparation of thorium(IV) alkoxide, amide, and organometallic compounds.

  8. CNN pincer ruthenium catalysts for hydrogenation and transfer hydrogenation of ketones: experimental and computational studies.

    PubMed

    Baratta, Walter; Baldino, Salvatore; Calhorda, Maria José; Costa, Paulo J; Esposito, Gennaro; Herdtweck, Eberhardt; Magnolia, Santo; Mealli, Carlo; Messaoudi, Abdelatif; Mason, Sax A; Veiros, Luis F

    2014-10-13

    Reaction of [RuCl(CNN)(dppb)] (1-Cl) (HCNN=2-aminomethyl-6-(4-methylphenyl)pyridine; dppb=Ph2 P(CH2 )4 PPh2 ) with NaOCH2 CF3 leads to the amine-alkoxide [Ru(CNN)(OCH2 CF3 )(dppb)] (1-OCH2 CF3 ), whose neutron diffraction study reveals a short RuO⋅⋅⋅HN bond length. Treatment of 1-Cl with NaOEt and EtOH affords the alkoxide [Ru(CNN)(OEt)(dppb)]⋅(EtOH)n (1-OEt⋅n EtOH), which equilibrates with the hydride [RuH(CNN)(dppb)] (1-H) and acetaldehyde. Compound 1-OEt⋅n EtOH reacts reversibly with H2 leading to 1-H and EtOH through dihydrogen splitting. NMR spectroscopic studies on 1-OEt⋅n EtOH and 1-H reveal hydrogen bond interactions and exchange processes. The chloride 1-Cl catalyzes the hydrogenation (5 atm of H2 ) of ketones to alcohols (turnover frequency (TOF) up to 6.5×10(4) h(-1) , 40 °C). DFT calculations were performed on the reaction of [RuH(CNN')(dmpb)] (2-H) (HCNN'=2-aminomethyl-6-(phenyl)pyridine; dmpb=Me2 P(CH2 )4 PMe2 ) with acetone and with one molecule of 2-propanol, in alcohol, with the alkoxide complex being the most stable species. In the first step, the Ru-hydride transfers one hydrogen atom to the carbon of the ketone, whereas the second hydrogen transfer from NH2 is mediated by the alcohol and leads to the key "amide" intermediate. Regeneration of the hydride complex may occur by reaction with 2-propanol or with H2 ; both pathways have low barriers and are alcohol assisted.

  9. Polyelectrolyte complex/PVA membranes for diffusion dialysis.

    PubMed

    Wang, Cong; Wu, Cuiming; Wu, Yonghui; Gu, Jingjing; Xu, Tongwen

    2013-10-15

    Polyelectrolyte complexes (PECs)/polyvinyl alcohol (PVA) membranes are prepared from PVA, anion exchange and cation exchange multisilicon copolymers, which contain plenty of functional groups of OH, N(+)(CH3)3/Si(OCH3)3, and SO3Na/Si(OCH3)3, respectively. The OH and Si(OCH3)3 groups can undertake sol-gel reaction to form crosslinking structure, while the N(+)(CH3)3 and SO3Na groups can be combined through electrostatic interaction. The PECs/PVA membranes exhibit improved thermal stability, swelling resistance and flexibility as compared with single anion or cation exchange hybrid membranes. The PECs/PVA membranes have the water uptakes (WR) of 25.3-70.4%, initial decomposition temperatures (IDTs) of 246-285°C, tensile strength of 23.1-33.8 MPa, and elongation at break of 3.5-13.1%. The membranes can be potentially applied for both acid and alkali recovery through diffusion dialysis (DD) process. The separation factor (S) for HCl/FeCl2 mixture can reach up to 89.9, which is about five times higher than that of commercial DF-120 membrane (18.5 at 25°C). The dialysis coefficients of NaOH (UOH) are in the range of 0.014-0.019 m/h, around 7-9 times higher than the value of commercial SPPO membrane (0.002 m/h at 25°C). The membranes also show potential usefulness for industrial acidic and alkali wastes treatment.

  10. Rate constants for the reaction of OH radicals with n-propyl, n-butyl, iso-butyl and tert-butyl vinyl ethers

    NASA Astrophysics Data System (ADS)

    Thiault, G.; Mellouki, A.

    Rate constants for the reaction of OH radicals with n-propyl vinyl ether (PVE, CH 3CH 2CH 2OCH dbnd CH 2), n-butyl vinyl ether (BVE, CH 3CH 2CH 2CH 2OCH dbnd CH 2), iso-butyl vinyl ether (IBVE, (CH 3) 2CHCH 2OCH dbnd CH 2) and tert-butyl vinyl ether (TBVE, (CH 3) 3COCH dbnd CH 2), have been measured in the temperature and pressure ranges 232-373 K and 30-300 Torr using the pulsed laser photolysis-laser-induced fluorescence method, and at 298 K and 760 Torr using the relative method. The obtained results are k1=(9.3±0.6)×10 -12 exp[(708±20)/ T], k2=(1.5±0.2)×10 -11 exp[(572±42)/ T], k3=(1.6±0.1)×10 -11 exp[(567±20)/ T], k4=(1.7±0.2)×10 -11 exp[(549±25)/ T] cm 3 molecule -1 s -1. The values at 298 K are k1=(1.0±0.1)×10 -10, k2=(1.0±0.1)×10 -10, k3=(1.1±0.1)×10 -10, k4=(1.1±0.1)×10 -10 cm 3 molecule -1 s -1. The deduced tropospheric lifetimes of these ethers for reaction with OH are of the order of 1 h and they are comparable to those for reaction with ozone.

  11. Probe electrospray ionization (PESI) mass spectrometry with discontinuous atmospheric pressure interface (DAPI).

    PubMed

    Hiraoka, Kenzo; Usmanov, Dilshadbek T; Chen, Lee Chuin; Ninomiya, Satoshi; Mandal, Mridul K; Saha, Subhrakanti

    2015-01-01

    Probe electrospray ionization (PESI) using a 0.2 mm outside diameter titanium wire was performed and the generated ions were introduced into the mass spectrometer via a discontinuous atmospheric pressure interface using a pinch valve. Time-lapse PESI mass spectra were acquired by gradually increasing delay time for the pinch valve opening with respect to the start of each electrospray event when a high voltage was applied. The opening time of the pinch valve was 20 ms. Time-resolved PESI mass spectra showed marked differences for 10 mM NaCl, 10(-5) M gramicidin S and insulin in H(2)O/CH(3)OH/CH(3)COOH/CH(3)COONH(4) (65/35/1) with and without the addition of 10 mM CH(3)COONH(4). This was ascribed to the pH change of the liquid attached to the needle caused by electrochemical reactions taking place at the interface between the metal probe and the solution. NaCl cluster ions appeared only after the depletion of analytes. For the mixed solution of 10(-5) M cytochrome c, insulin, and gramicidin S in H(2)O/CH(3)OH/CH(3)COOH (65/35/1), a sequential appearance of analyte ions in the order of cytochrome c→insulin→gramicidin S was observed. The present technique was applied to three narcotic samples; methamphetamine, morphine and codeine. Limits of detection for these compounds were 10 ppb in H(2)O/CH(3)OH (1/1) for the single sampling with a pinch valve opening time of 200 ms.

  12. Synthesis of a TREN in which the aryl substituents are part of a 45 atom macrocycle.

    PubMed

    Cain, Matthew F; Forrest, William P; Peryshkov, Dmitry V; Schrock, Richard R; Müller, Peter

    2013-10-16

    A substituted TREN has been prepared in which the aryl groups in (ArylNHCH2CH2)3N are substituted at the 3- and 5-positions with a total of six OCH2(CH2)nCH═CH2 groups (n = 1, 2, 3). Molybdenum nitride complexes, [(ArylNCH2CH2)3N]Mo(N), have been isolated as adducts that contain B(C6F5)3 bound to the nitride. Two of these [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) complexes (n = 1 and 3) were crystallographically characterized. After removal of the borane from [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) with PMe3, ring-closing olefin metathesis (RCM) was employed to join the aryl rings with OCH2(CH2)nCH═CH(CH2)nCH2O links (n = 1-3) between them. RCM worked best with a W(O)(CHCMe3)(Me2Pyr)(OHMT)(PMe2Ph) catalyst (OHMT = hexamethylterphenoxide, Me2Pyr = 2,5-dimethylpyrrolide) and n = 3. The macrocyclic ligand was removed from the metal through hydrolysis and isolated in 70-75% yields relative to the borane adducts. Crystallographic characterization showed that the macrocyclic TREN ligand in which n = 3 contains three cis double bonds. Hydrogenation produced a TREN in which the three links are saturated, i.e., O(CH2)10O.

  13. Surface characterization of biocidal polyurethane modifiers having poly(3,3-substituted)oxetane soft blocks with alkylammonium side chains.

    PubMed

    Kurt, Pinar; Gamble, Lara J; Wynne, Kenneth J

    2008-06-03

    This paper focuses on surface characterization of P[ AB] copolyoxetane soft block polyurethanes having either fluorous (3FOx, -CH2OCH 2CF3) or PEG-like (ME2Ox, -CH2(OCH2CH2) 2OCH3), A side chains and alkylammonium, B side chains. Physical surface characterization data were analyzed in light of the previously observed order of antimicrobial effectiveness for a set of four surface modifiers. Ample physical evidence for surface concentration of fluorous 2 wt % P[ AB]-polyurethane modifiers was obtained from XPS, contact angles, ATR-IR spectroscopy, and TM-AFM. In TM-AFM phase imaging, the most effective biocidal surface modifier, 2 wt % HMDI-BD(30)/P[(3FOx)(C12)-0.89:0.11]-PU, showed a nanoscale phase-separated structure consisting of 200 nm domains with background features about 10 times smaller. Despite similar surface characterization data, the 2 wt % fluorous C6 analog ranked third in contact biocidal effectiveness. Physical evidence for surface concentration of 2 wt % P[(ME2Ox)(C12)-0.86:0.14]-PU was modest, considering that antimicrobial effectiveness was second only to 2 wt % HMDI-BD(30)/P[(3FOx)(C12)-0.89:0.11]-PU. In this set of surface modifiers, nanoscale morphology is largely driven by the fluorous component, whereas antimicrobial effectiveness is more strongly influenced by alkylammonium chain length. The effect of alkylammonium side chain length on surface concentration and antimicrobial behavior is more pronounced for ME2Ox polyurethanes compared to the 3FOx analogs.

  14. Slip Rate Determination of Thrusts Along the Edge of NE Tibet From in situ-Produced Cosmogenic Nuclides

    NASA Astrophysics Data System (ADS)

    Hetzel, R.; Niedermann, S.; Tao, M.; Ivy-Ochs, S.; Stokes, S.; Strecker, M. R.; Kubik, P. W.

    2005-12-01

    The Qilian Shan forms a seismically active fold-and-thrust-belt along the NE margin of the Tibetan Plateau that evolved during the Neogene-Quaternary and continues to advance north-northeastward (Meyer et al., 1998; Tapponnier et al., 2001). Active thrust faults transecting Late Pleistocene alluvial fan deposits form spectacular fault scarps that are locally incised by rivers which form flights of terraces. By combining structural investigations, satellite imagery, topographic profiling, surface exposure, and luminescence dating we have determined slip rates for several thrust faults (Hetzel et al. 2002, 2004a,b). Our results are consistent with geologic and GPS constraints, which suggest that NNE-directed shortening across the northeastern Tibetan Plateau is distributed on several active faults with a total shortening rate of about 4 to 10 mm/yr. References Hetzel, R., S. Niedermann, M. Tao, P.W. Kubik, S. Ivy-Ochs, B. Gao, M.R. Strecker (2002a), Nature, 417, 428-432. Hetzel, R., M. Tao, S. Niedermann, M.R. Strecker, S. Ivy-Ochs, P.W. Kubik, B. Gao (2004a), Terra Nova 16, 157-162. Hetzel R., M. Tao, S. Stokes, S. Niedermann, S. Ivy-Ochs, G. Bo, M.R. Strecker, P.W. Kubik (2004b), Tectonics 23, TC6006, doi:10.1029/2004TC001653. Meyer, B., P. Tapponnier, L. Bourjot, F. Metivier, Y. Gaudemer, G. Peltzer, G. Shunmin, C. Zhitai (1998), Geophys. J. Int., 135, 1-47. Tapponnier, P., Z. Xu, F. Roger, B. Meyer, N. Arnaud, G. Wittlinger, J. Yang (2001), Science, 294, 1671-1677.

  15. Synthesis, characteristic and theoretical investigation of the structure, electronic properties and second-order nonlinearity of salicylaldehyde Schiff base and their derivatives

    NASA Astrophysics Data System (ADS)

    Tang, Guo-Dong; Zhao, Jian-Ying; Li, Rong-Qing; Yuan-Cao; Zhang, Zai-Chao

    2011-01-01

    A series of asymmetric donor-acceptor substituted salen-type Schiff-bases have been synthesized and their structures, electronic properties and second order nonlinearities were investigated by DFT methods. In order to verify the stable of these Schiff-base derivates, the IR spectrum of these Schiff-base derivates were calculated, the result showed that these compounds are stable. The results of TD-DFT calculation indicate that the derivatives with the electron-donating group (CH 3, OCH 3 or N(C 2H 5) 2) have a red shift absorption compared to derivatives with the electron-withdrawing group (NO 2). The analysis of MOS indicates that the CN group has contribution to the LUMO orbital while the groups of OCH 3, N(C 2H 5) 2 and NO 2 have contribution to the HOMO orbital. OCH 3, N(C 2H 5) 2 as electron rich groups, made the derivates have a larger first static hyperpolarizability. However, the compound (II) with a NO 2 substituent, also has a large first static hyperpolarizability. This is probably because of the special transition model, namely the values of two oscillator strength f ( fHOMO-1-LUMO = 0.405, fHOMO-LUMO = 0.321) are almost equal. In order to understand the influence of the energy gap (Δ E) between the HOMO and the LUMO orbitals on the first static hyperpolarizability, we calculated the energy gap (Δ E) of all Schiff-base compounds. The results show that the smaller the HOMO-LUMO energy gap is, the larger the first static hyperpolarizability is.

  16. Hydrogen-bonding Interactions between Apigenin and Ethanol/Water: A Theoretical Study

    PubMed Central

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui; Lai, Rong-Cai

    2016-01-01

    In this work, hydrogen-bonding interactions between apigenin and water/ethanol were investigated from a theoretical perspective using quantum chemical calculations. Two conformations of apigenin molecule were considered in this work. The following results were found. (1) For apigenin monomer, the molecular structure is non-planar, and all of the hydrogen and oxygen atoms can be hydrogen-bonding sites. (2) Eight and seven optimized geometries are obtained for apigenin (I)–H2O/CH3CH2OH and apigenin (II)–H2O/CH3CH2OH complexes, respectively. In apigenin, excluding the aromatic hydrogen atoms in the phenyl substituent, all other hydrogen atoms and the oxygen atoms form hydrogen-bonds with H2O and CH3CH2OH. (3) In apigenin–H2O/CH3CH2OH complexes, the electron density and the E(2) in the related localized anti-bonding orbital are increased upon hydrogen-bond formation. These are the cause of the elongation and red-shift of the X−H bond. The sum of the charge change transfers from the hydrogen-bond acceptor to donor. The stronger interaction makes the charge change more intense than in the less stable structures. (4) Most of the hydrogen-bonds in the complexes are electrostatic in nature. However, the C4−O5···H, C9−O4···H and C13−O2···H hydrogen-bonds have some degree of covalent character. Furthermore, the hydroxyl groups of the apigenin molecule are the preferred hydrogen-bonding sites. PMID:27698481

  17. Formation of Polyhydroxyalkanoate in Aerobic Anoxygenic Phototrophic Bacteria and Its Relationship to Carbon Source and Light Availability▿

    PubMed Central

    Xiao, Na; Jiao, Nianzhi

    2011-01-01

    Aerobic anoxygenic phototrophic bacteria (AAPB) are unique players in carbon cycling in the ocean. Cellular carbon storage is an important mechanism regulating the nutrition status of AAPB but is not yet well understood. In this paper, six AAPB species (Dinoroseobacter sp. JL1447, Roseobacter denitrificans OCh 114, Roseobacter litoralis OCh 149, Dinoroseobacter shibae DFL 12T, Labrenzia alexandrii DFL 11T, and Erythrobacter longus DSMZ 6997) were examined, and all of them demonstrated the ability to form the carbon polymer polyhydroxyalkanoate (PHA) in the cell. The PHA in Dinoroseobacter sp. JL1447 was identified as poly-beta-hydroxybutyrate (PHB) according to evidence from Fourier transform infrared spectroscopy, differential scanning calorimetry, and 1H nuclear magnetic resonance spectroscopy examinations. Carbon sources turned out to be critical for PHA production in AAPB. Among the eight media tested with Dinoroseobacter sp. JL1447, sodium acetate, giving a PHA production rate of 72%, was the most productive carbon source, followed by glucose, with a 68% PHA production rate. Such PHA production rates are among the highest recorded for all bacteria. The C/N ratio of substrates was verified by the experiments as another key factor in PHA production. In the case of R. denitrificans OCh 114, PHA was not detected when the organism was cultured at C/N ratios of <2 but became apparent at C/N ratios of >3. Light is also important for the formation of PHA in AAPB. In the case of Dinoroseobacter sp. JL1447, up to a one-quarter increase in PHB production was observed when the culture underwent growth in a light-dark cycle compared to growth completely in the dark. PMID:21908634

  18. Reversible potentials for steps in methanol and formic acid oxidation to CO2; adsorption energies of intermediates on the ideal electrocatalyst for methanol oxidation and CO2 reduction.

    PubMed

    Anderson, Alfred B; Asiri, Haleema Aied

    2014-06-14

    Quantum chemical theory is used to identify the reasons for platinum's limitations as an electrocatalyst for oxidizing methanol at fuel cell anodes. The linear Gibbs energy relation (LGER) method is employed to predict reversible potentials for reaction steps for intermediates on the electrode surface. In this procedure, standard reversible potentials are calculated for the reactions in bulk solution phase and then they are perturbed using calculated adsorption bond strengths to the electrode surface, yielding the equilibrium potentials for each electron transfer step for adsorbed intermediates. Adsorption properties of ideal electrocatalysts for the methanol oxidation are found by imposing the condition that the reversible potential of each electron transfer step equals that for the overall reaction. The adsorption bond strengths that provide the ideal properties also apply to formic acid oxidation and carbon dioxide reduction. It is instructive to think of the ideal electrocatalyst as a lens that focusses the reversible potentials for the n individual electron transfer steps to the reversible potential for the n-electron process. It is found that the ideal catalyst will adsorb many intermediates, including HOOC, CO, OCH, HOC, HOCH, HOCH2, and OCH3 more weakly than platinum, and OOCH and OH more strongly. For example, for one possible pathway it is necessary to weaken adsorption bond strengths for HOCH2, HOCH, OCH, HOOC by about 0.5 eV, weaken adsorption CO by about 1.1 eV and strengthen OH adsorption by about 0.6 eV. These results imply a need for developing new multi-component catalysts.

  19. Phospholipase C and myosin light chain kinase inhibition define a common step in actin regulation during cytokinesis

    PubMed Central

    Wong, Raymond; Fabian, Lacramioara; Forer, Arthur; Brill, Julie A

    2007-01-01

    Background Phosphatidylinositol 4,5-bisphosphate (PIP2) is required for successful completion of cytokinesis. In addition, both PIP2 and phosphoinositide-specific phospholipase C (PLC) have been localized to the cleavage furrow of dividing mammalian cells. PLC hydrolyzes PIP2 to yield diacylglycerol (DAG) and inositol trisphosphate (IP3), which in turn induces calcium (Ca2+) release from the ER. Several studies suggest PIP2 must be hydrolyzed continuously for continued cleavage furrow ingression. The majority of these studies employ the N-substituted maleimide U73122 as an inhibitor of PLC. However, the specificity of U73122 is unclear, as its active group closely resembles the non-specific alkylating agent N-ethylmaleimide (NEM). In addition, the pathway by which PIP2 regulates cytokinesis remains to be elucidated. Results Here we compared the effects of U73122 and the structurally unrelated PLC inhibitor ET-18-OCH3 (edelfosine) on cytokinesis in crane-fly and Drosophila spermatocytes. Our data show that the effects of U73122 are indeed via PLC because U73122 and ET-18-OCH3 produced similar effects on cell morphology and actin cytoskeleton organization that were distinct from those caused by NEM. Furthermore, treatment with the myosin light chain kinase (MLCK) inhibitor ML-7 caused cleavage furrow regression and loss of both F-actin and phosphorylated myosin regulatory light chain from the contractile ring in a manner similar to treatment with U73122 and ET-18-OCH3. Conclusion We have used multiple inhibitors to examine the roles of PLC and MLCK, a predicted downstream target of PLC regulation, in cytokinesis. Our results are consistent with a model in which PIP2 hydrolysis acts via Ca2+ to activate myosin via MLCK and thereby control actin dynamics during constriction of the contractile ring. PMID:17509155

  20. Phospholipase C and myosin light chain kinase inhibition define a common step in actin regulation during cytokinesis.

    PubMed

    Wong, Raymond; Fabian, Lacramioara; Forer, Arthur; Brill, Julie A

    2007-05-17

    Phosphatidylinositol 4,5-bisphosphate (PIP2) is required for successful completion of cytokinesis. In addition, both PIP2 and phosphoinositide-specific phospholipase C (PLC) have been localized to the cleavage furrow of dividing mammalian cells. PLC hydrolyzes PIP2 to yield diacylglycerol (DAG) and inositol trisphosphate (IP3), which in turn induces calcium (Ca2+) release from the ER. Several studies suggest PIP2 must be hydrolyzed continuously for continued cleavage furrow ingression. The majority of these studies employ the N-substituted maleimide U73122 as an inhibitor of PLC. However, the specificity of U73122 is unclear, as its active group closely resembles the non-specific alkylating agent N-ethylmaleimide (NEM). In addition, the pathway by which PIP2 regulates cytokinesis remains to be elucidated. Here we compared the effects of U73122 and the structurally unrelated PLC inhibitor ET-18-OCH3 (edelfosine) on cytokinesis in crane-fly and Drosophila spermatocytes. Our data show that the effects of U73122 are indeed via PLC because U73122 and ET-18-OCH3 produced similar effects on cell morphology and actin cytoskeleton organization that were distinct from those caused by NEM. Furthermore, treatment with the myosin light chain kinase (MLCK) inhibitor ML-7 caused cleavage furrow regression and loss of both F-actin and phosphorylated myosin regulatory light chain from the contractile ring in a manner similar to treatment with U73122 and ET-18-OCH3. We have used multiple inhibitors to examine the roles of PLC and MLCK, a predicted downstream target of PLC regulation, in cytokinesis. Our results are consistent with a model in which PIP2 hydrolysis acts via Ca2+ to activate myosin via MLCK and thereby control actin dynamics during constriction of the contractile ring.

  1. Kinetics of the degradation of sulfur mustard on ambient and moist concrete.

    PubMed

    Brevett, Carol A S; Sumpter, Kenneth B; Nickol, Robert G

    2009-02-15

    The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using (13)C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 degrees C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 degrees C ranged from 75 to 350h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 degrees C and weeks to months on concrete at 35 degrees C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane.

  2. Searching for trans ethyl methyl ether in Orion KL(.)

    PubMed

    Tercero, B; Cernicharo, J; López, A; Brouillet, N; Kolesniková, L; Motiyenko, R A; Margulès, L; Alonso, J L; Guillemin, J-C

    2015-10-01

    We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 10(15) cm(-2) and ≤(1.0 ± 0.2)× 10(15) cm(-2) for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion.

  3. An OEGylated thiol monolayer for the tethering of liposomes and the study of liposome interactions.

    PubMed

    Briand, Elisabeth; Humblot, Vincent; Pradier, Claire-Marie; Kasemo, Bengt; Svedhem, Sofia

    2010-06-15

    The aim of the present work is to develop a protocol for the specific immobilization of liposomes, via tethers, onto functionalized gold surfaces, and in addition to give one example for such a surface architecture. All surface functionalization steps are charcerized and controlled. First, mixed thiolate self-assembled monolayers (SAMs) prepared from COOH- and OCH(3)-terminated oligo(ethylene glycol) (OEG) alkane thiols were characterized by polarization modulation reflection absorption infrared spectroscopy (PM-RAIRS) and by X-ray photoemission spectroscopy (XPS). The composition of the mixed SAMs was found to be close to that of the thiol solution. Next, grafting of biotin conjugated with an NH(2)-terminated OEG spacer (biotin-OEG-NH(2)) to the COOH groups via conventional amine coupling was optimized with respect to the COOH/OCH(3) ratio of the SAM. The grafting of biotin-OEG-NH(2) was assessed by monitoring the binding of neutravidin and albumin to the biotinylated surfaces using quartz crystal microbalance with dissipation monitoring (QCM-D), as well as by PM-RAIRS. It was shown that a COOH/OCH(3) ratio of around 0.3 was sufficient to saturate the SAMs with neutravidin. Finally, tethering of liposomes onto the neutravidin-terminated SAMs, was achieved. As an application example, of a close packed layer of tethered liposomes was exposed to the membrane-penetrating peptide melittin. As monitored by QCM-D, the liposomes fused when interacting with the peptide and ruptured into an extended, supported lipid bilayer over the whole surface. In summary, the described surface modification has potential for the development of assays requiring tethered intact liposomes, or tethered planar bilayers. Such surface architectures are especially important for the study of transmembrane proteins and peptides.

  4. New 3D structuring process for non-integrated circuit related technologies (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Nouri, Lamia; Possémé, Nicolas; Landis, Stéfan; Milesi, Frédéric; Gaillard, Frédéric-Xavier

    2017-04-01

    Fabrication processes that microelectronic developed for Integrated circuit (IC) technologies for decades, do not meet the new emerging structuration's requirements, in particular non-IC related technologies one, such as MEMS/NEMS, Micro-Fluidics, photovoltaics, lenses. Actually complex 3D structuration requires complex lithography patterning approaches such as gray-scale electron beam lithography, laser ablation, focused ion beam lithography, two photon polymerization. It is now challenging to find cheaper and easiest technique to achieve 3D structures. In this work, we propose a straightforward process to realize 3D structuration, intended for silicon based materials (Si, SiN, SiOCH). This structuration technique is based on nano-imprint lithography (NIL), ion implantation and selective wet etching. In a first step a pattern is performed by lithography on a substrate, then ion implantation is realized through a resist mask in order to create localized modifications in the material, thus the pattern is transferred into the subjacent layer. Finally, after the resist stripping, a selective wet etching is carried out to remove selectively the modified material regarding the non-modified one. In this paper, we will first present results achieved with simple 2D line array pattern processed either on Silicon or SiOCH samples. This step have been carried out to demonstrate the feasibility of this new structuration process. SEM pictures reveals that "infinite" selectivity between the implanted areas versus the non-implanted one could be achieved. We will show that a key combination between the type of implanted ion species and wet etching chemistries is required to obtain such results. The mechanisms understanding involved during both implantation and wet etching processes will also be presented through fine characterizations with Photoluminescence, Raman and Secondary Ion Mass Spectrometry (SIMS) for silicon samples, and ellipso-porosimetry and Fourier Transform Infra

  5. Dinuclear titanium(IV) complexes from amino acid bridged dicatechol ligands: formation, structure, and conformational analysis.

    PubMed

    Albrecht, M; Napp, M; Schneider, M; Weis, P; Fröhlich, R

    2001-09-17

    Amino acid bridged dicatechol ligands 3a-e-H4 form dinuclear double-stranded coordination compounds [(3a-e)2Ti2(OCH3)2]2- with titanium(IV) ions. Due to the directionality of the ligands, the chirality of the strand, and the chiral complex units, up to seven isomers, I-VII, can be obtained for the double-stranded complexes of ligands 3a-e-H4. The composition of the mixture of isomeric compounds in solution is strongly dependent on the conditions of complex formation. Under thermodynamic control, only a few isomers are obtained, one of which is the major component of the mixture. X-ray structure analyses were performed for K2[(3b)2Ti2(OH)2] and K2[(3d)2Ti2(OH)2] (type I), and for the meso complex Na2[(3e)(3e')Ti2(OCH3)2]. A conformational analysis that uses Ramachandrans method revealed that the conformation of the amino acids in the ligand strands can be compared with those found for amino acids in helical peptide structures. The most favored isomer of [(3)2Ti2(OCH3)2]2- appears to be of type I, with the catecholamide unit located at the N terminus of the ligand strand that binds to a lambda-configurated titanium(IV) complex unit and the dihydroxybenzyl group at the C terminus that coordinates to a delta-configurated titanium(IV) complex unit. The lambda configuration at the N terminus induces the conformation of a right-handed helix in the amino acid residue, while the delta configuration induces the less favored left-handed helix.

  6. Synthesis, characteristic and theoretical investigation of the structure, electronic properties and second-order nonlinearity of salicylaldehyde Schiff base and their derivatives.

    PubMed

    Tang, Guo-Dong; Zhao, Jian-Ying; Li, Rong-Qing; Yuan-Cao; Zhang, Zai-Chao

    2011-01-01

    A series of asymmetric donor-acceptor substituted salen-type Schiff-bases have been synthesized and their structures, electronic properties and second order nonlinearities were investigated by DFT methods. In order to verify the stable of these Schiff-base derivates, the IR spectrum of these Schiff-base derivates were calculated, the result showed that these compounds are stable. The results of TD-DFT calculation indicate that the derivatives with the electron-donating group (CH3, OCH3 or N(C2H5)2) have a red shift absorption compared to derivatives with the electron-withdrawing group (NO2). The analysis of MOS indicates that the CN group has contribution to the LUMO orbital while the groups of OCH3, N(C2H5)2 and NO2 have contribution to the HOMO orbital. OCH3, N(C2H5)2 as electron rich groups, made the derivates have a larger first static hyperpolarizability. However, the compound (II) with a NO2 substituent, also has a large first static hyperpolarizability. This is probably because of the special transition model, namely the values of two oscillator strength f (fHOMO-1-LUMO=0.405, fHOMO-LUMO=0.321) are almost equal. In order to understand the influence of the energy gap (ΔE) between the HOMO and the LUMO orbitals on the first static hyperpolarizability, we calculated the energy gap (ΔE) of all Schiff-base compounds. The results show that the smaller the HOMO-LUMO energy gap is, the larger the first static hyperpolarizability is.

  7. Preventing and curing citrulline-induced autoimmune arthritis in a humanized mouse model using a Th2-polarizing iNKT cell agonist.

    PubMed

    Walker, Kyle M; Rytelewski, Mateusz; Mazzuca, Delfina M; Meilleur, Shannon A; Mannik, Lisa A; Yue, David; Brintnell, William C; Welch, Ian; Cairns, Ewa; Haeryfar, S M Mansour

    2012-07-01

    Invariant natural killer T (iNKT) cells are innate lymphocytes with unique reactivity to glycolipid antigens bound to non-polymorphic CD1d molecules. They are capable of rapidly releasing pro- and/or anti-inflammatory cytokines and constitute attractive targets for immunotherapy of a wide range of diseases including autoimmune disorders. In this study, we have explored the beneficial effects of OCH, a Th2-polarizing glycolipid agonist of iNKT cells, in a humanized mouse model of rheumatoid arthritis (RA) in which citrullinated human proteins are targeted by autoaggressive immune responses in mice expressing an RA susceptibility human leukocyte antigen (HLA) DR4 molecule. We found for the first time that treatment with OCH both prevents and cures citrulline-induced autoimmune arthritis as evidenced by resolved ankle swelling and reversed histopathological changes associated with arthritis. Also importantly, OCH treatment blocked the arthritogenic capacity of citrullinated antigen-experienced splenocytes without compromising their global responsiveness or altering the proportion of splenic naturally occurring CD4(+)CD25(+)FoxP3(+) regulatory T cells. Interestingly, administering the Th1-promoting iNKT cell glycolipid ligand α-C-galactosylceramide into HLA-DR4 transgenic mice increased the incidence of arthritis in these animals and exacerbated their clinical symptoms, strongly suggesting a role for Th1 responses in the pathogenesis of citrulline-induced arthritis. Therefore, our findings indicate a role for Th1-mediated immunopathology in citrulline-induced arthritis and provide the first evidence that iNKT cell manipulation by Th2-skewing glycolipids may be of therapeutic value in this clinically relevant model, a finding that is potentially translatable to human RA.

  8. Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether.

    PubMed

    Moshammer, Kai; Jasper, Ahren W; Popolan-Vaida, Denisia M; Lucassen, Arnas; Diévart, Pascal; Selim, Hatem; Eskola, Arkke J; Taatjes, Craig A; Leone, Stephen R; Sarathy, S Mani; Ju, Yiguang; Dagaut, Philippe; Kohse-Höinghaus, Katharina; Hansen, Nils

    2015-07-16

    In this paper we report the detection and identification of the keto-hydroperoxide (hydroperoxymethyl formate, HPMF, HOOCH2OCHO) and other partially oxidized intermediate species arising from the low-temperature (540 K) oxidation of dimethyl ether (DME). These observations were made possible by coupling a jet-stirred reactor with molecular-beam sampling capabilities, operated near atmospheric pressure, to a reflectron time-of-flight mass spectrometer that employs single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation. On the basis of experimentally observed ionization thresholds and fragmentation appearance energies, interpreted with the aid of ab initio calculations, we have identified HPMF and its conceivable decomposition products HC(O)O(O)CH (formic acid anhydride), HC(O)OOH (performic acid), and HOC(O)OH (carbonic acid). Other intermediates that were detected and identified include HC(O)OCH3 (methyl formate), cycl-CH2-O-CH2-O- (1,3-dioxetane), CH3OOH (methyl hydroperoxide), HC(O)OH (formic acid), and H2O2 (hydrogen peroxide). We show that the theoretical characterization of multiple conformeric structures of some intermediates is required when interpreting the experimentally observed ionization thresholds, and a simple method is presented for estimating the importance of multiple conformers at the estimated temperature (∼100 K) of the present molecular beam. We also discuss possible formation pathways of the detected species: for example, supported by potential energy surface calculations, we show that performic acid may be a minor channel of the O2 + ĊH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OĊHOOH intermediate, which predominantly leads to the HPMF.

  9. The effect of solution chemistry on the preparation of MgAl{sub 2}O{sub 4} by hydrothermal-assisted sol-gel processing

    SciTech Connect

    Amini, M.M. . E-mail: m-pouramini@cc.sbu.ac.ir; Mirzaee, M.; Sepanj, N.

    2007-03-22

    Preparation of magnesium aluminate spinel powder by hydrothermal-assisted sol-gel processing from MgAl{sub 2}(OCH{sub 2}CH{sub 2}OR){sub 8}, R=CH{sub 3} (1), CH{sub 2}CH{sub 2}OCH{sub 3} (2), MgAl{sub 2}[OCH(CH{sub 3}){sub 2}]{sub 8} (3) and MgAl{sub 2}(O- {sup s}Bu){sub 8} (4) in toluene and parent alcohol has been investigated. Coordination status of aluminum atom in precursors was determined by {sup 27}Al NMR and correlation between coordination number of aluminum and development of spinel phase in hydrothermal-assisted sol-gel processing has been studied. The gels obtained from hydrothermal-assisted hydrolysis of magnesium-aluminum alkoxides that contain six-coordinated aluminum atoms in solution (1 and 2) after calcination at 700 deg. C resulted in the formation of pure spinel phase, whereas in similar hydrolysis and calcination processes of precursors that contain four-coordinated aluminum (3 and 4) spinel phase forms along with some Al{sub 2}O{sub 3} and MgO. Selected powders obtained from hydrothermal-assisted sol-gel processing were characterized by thermal analysis (TGA/DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Results indicate that the coordination status of aluminum in the precursor is very crucial for the formation of pure phase spinel. The morphology of prepared spinels was studied by SEM and the results showed that the solvent in hydrothermal-assisted sol-gel processing has a marked effect on the morphology of the resulting MgAl{sub 2}O{sub 4}. In hydrothermal-assisted sol-gel processing of aluminum-magnesium alkoxides in hydrophobic solvent, spherical particles are formed, while in the parent alcohol, non-spherical powders are formed.

  10. Characterization of the Chemical Constitution and Profile of Pharmacological Activity of PGBx.

    DTIC Science & Technology

    1980-04-30

    DO-- Na- 1) C2 H 0 2CCHCOCH3 2) NaOCH3 CH 302C-CH2CO(CH2 )7CO2 CH3 6 Azelaic acid mono methyl ester 7 obtained commercially is converted to the acid ...testing a variety of separa- tion methods that he was familiar with. The sample of PGBx ( acid form) that was used in this study was that prepared and...solvent system of water--acetonitrile--chloro- form--acetic acid (76.7:23:0.2:0.1) gave two peaks, one with retention time of 1 min, the other 4.3 min

  11. The Formation of N- and O-Heterocycles from the Irradiation of Benzene and Naphthalene in H2O/NH3- Containing Ices

    NASA Technical Reports Server (NTRS)

    Sandford, S. A.; Materese, C. K.; Nuevo, M.

    2015-01-01

    Aromatic hydrocarbons are an important class of molecules for both astrochemistry and astrobiology (Fig. 1). Within this class of molecules, polycyclic aromatic hydrocarbons (PAHs) are known to be ubiquitous in many astrophysical environments, and are likely present in interstellar clouds and protostellar disks. In dense clouds, PAHs are expected to condense onto grains as part of mixed molecular ice mantles dominated by small molecules like H2O,CH3OH, NH3, CO, and CO2. These ices are exposed to ionizing radiation in the form of cosmic rays and ambient high-energy X-ray and UV photons.

  12. Contact sensitivity to nonoxynols as a cause of intolerance to antiseptic preparations.

    PubMed

    Dooms-Goossens, A; Deveylder, H; de Alam, A G; Lachapelle, J M; Tennstedt, D; Degreef, H

    1989-10-01

    Twelve cases of allergic contact dermatitis caused by antiseptic preparations are presented. The reactions resulted not from the active principles but rather from nonoxynols used in the offending substances as nonionic surface-active agents. Nonoxynols are ethoxylated alkyl phenols or nonylphenylethers that conform in general to the formula C9H19C6H4(OCH2CH2)nOH. They have emulsifying, wetting, foaming, and solubilizing properties and are used in a large number of industrial, household, agricultural, cosmetic, and pharmaceutical products. They also are used as spermicides. There are very few reports in the literature of skin problems caused by nonoxynols.

  13. Viscosity of Metals in Explosion Welding

    DTIC Science & Technology

    1974-11-19

    bglish sin fin can coo tg tan ct cot oh sinh oh cooh th tanh cth ooth Bh ech cch coch arc sin ow 1 arc coo OO8ŕ arc tg tan-1 arc ctg oot ŕ are ec...30c1l arc cooe 080 ŕ arc oh minhŕ arc ch cooh - 1 are tim tan- arc oth coth-1 arc sch ch-1 arc och coch -1 rot curl Ig log FTD-HT-23-1992-74 ii GREEK

  14. Theoretical study of the pyrolysis of vanillin as a model of secondary lignin pyrolysis

    NASA Astrophysics Data System (ADS)

    Wang, Meng; Liu, Chao; Xu, Xiaoxiao; Li, Qibin

    2016-06-01

    The unimolecular and bimolecular decomposition reactions in processes of vanillin pyrolysis were theoretically investigated by employing density functional theory (DFT) method at M06-2X/6-31 G+(d,p) level. The result shows that the homolytic cleavage of O-CH3 bond could be the dominant initial step in the pyrolysis of vanillin. The hydrogen abstractions from functional groups of vanillin by the formed radicals play important roles in the formation of main products. Both formyl, hydroxyl and methoxyl group contribute to the formation of CO. Benzene is formed from the hydrogen addition reaction between hydrogen radical and phenol at high temperature.

  15. Research on Organofluorine Chemistry for 700 Degrees F Thermooxidative Stability

    DTIC Science & Technology

    1994-06-29

    8217) 4 NC-OC (CF’), CH, + NC- OCH2CF3 The products can be readily converted to amides , i.e., R-O CN H O,/KOH >C2H3OH 0()~ Conversion of these amides ...isopropyl)phenyl, pentamethylcyclopentadiene (Cp’), (b) highly substituted methyl systems, e.g., bis (trimethylsilyl)methyl and tris(trimethylsilyl)methyl... fluorosulfonyl derivatives, find application in the production of strong sulfonic acids, ion-exchange resins, surface active agents and perfluorinated

  16. FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms.

    PubMed

    Moreno, A; Gallego-Iniesta, M P; Taccone, R; Martín, M P; Cabañas, B; Salgado, M S

    2014-10-01

    Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298 ± 2 K) and atmospheric pressure (708 ± 8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm(3) molecule(-1) s(-1)): (3.27 ± 0.33) × 10(-11) and (4.43 ± 0.42) × 10(-11), for CH3CH═CHC(O)OCH3 and (CH3)2CH═CHC(O)OCH3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N2 and air were used as the bath gases. The following rate coefficients were obtained (in cm(3) molecule(-1) s(-1)): k3 (CH2═CHC(O)O(CH2)5CH3 + Cl) = (3.31 ± 0.31) × 10(-10), k4(CH2═CHC(O)OCH2CH(CH2CH3)(CH2)3CH3 + Cl) = (3.46 ± 0.31) × 10(-10), k5(CH2═CHC(O)O(CH2)5CH3 + OH) = (2.28 ± 0.23) × 10(-11), and k6(CH2═CHC(O)OCH2CH(CH2CH3)(CH2)3CH3 + OH) = (2.74 ± 0.26) × 10(-11). The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in -C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do

  17. Role of High-Affinity Oncostatin M Receptor in Prevention of Breast Cancer Cell Growth.

    DTIC Science & Technology

    1998-09-01

    signal transducer gpl30. J. Exp. Med. 179:1343-1347. 6. Horn, D., Fitzpatrick, W.C., Gompper , P.T., Ochs, V., Bolton-Hansen, M ., Zarling, J.M., Malik...sequencing. Cancer Research, 57:759-764, 1997. 16. Ueda, K., Fukushima, EL, Masliah, E ., Y., Iwai, A, Yoshimoto, M ., Otero, D.A., Kondo, J., Ihara, Y, and...differential cDNA sequencing. Cancer Researc 57:759-764, 1997. 4. Liu J. Streiff R, Vestal E , and Briggs M : Novel Mechanism of Transcriptional Activation

  18. On the family- and genus-series nomina in Gyrinidae Latreille, 1810 (Coleoptera, Adephaga).

    PubMed

    Gustafson, Grey T; Miller, Kelly B

    2013-10-29

    All available genus- and family- group nomina for the Gyrinidae (Coleoptera: Adephaga) are listed along with original citation, original and current status, type nominal taxon with method of designation, and known synonymies and incorrect subsequent spellings. The nomina included follow the most current classification. Discussion is provided clarifying numerous nomenclatural problems with original spellings, correct authorship and type designation. Dineutini Ochs, 1926 syn. nov. is found to be a junior homonym of Dineutini Desmarest, 1851, and Enhydrini Régimbart, 1882 syn. nov. and its justified emendation Enhydrusini (Anonymous 2012) are here synonymized with Dineutini Desmarest, 1851.

  19. Insight into selected reactions in low-temperature dimethyl ether combustion from Born-Oppenheimer molecular dynamics.

    PubMed

    Andersen, Amity; Carter, Emily A

    2006-02-02

    Dimethyl ether is under consideration as an alternative diesel fuel. Its combustion chemistry is as yet ill-characterized. Here we use Born-Oppenheimer molecular dynamics (BOMD) based on DFT-B3LYP forces to investigate the short-time dynamics of selected features of the low-temperature dimethyl ether (DME) oxidation potential energy surface. Along the chain propagation pathway, we run BOMD simulations from the transition state involving the decomposition of (*)CH(2)OCH(2)OOH to two CH(2)=O and an (*)OH radical. We predict that formaldehyde C-O stretch overtones are excited, consistent with laser photolysis experiments. We also predict that O-H overtones are excited for the (*)OH formed from (*)CH(2)OCH(2)OOH dissociation. We also investigate short-time dynamics involved in chain branching. First, we examine the isomerization transition state of (*)OOCH(2)OCH(2)OOH --> HOOCH(2)OCHOOH. The latter species is predicted to be a short-lived metastable radical that decomposes within 500 fs to hydroperoxymethyl formate (HPMF; HOOCH(2)OC(=O)H) and the first (*)OH of chain branching. The dissociation of HOOCH(2)OCHOOH exhibits non-RRKM behavior in its lifetime profile, which may be due to conformational constraints or slow intramolecular vibrational energy transfer (IVR) from the nascent H-O bond to the opposite end of the radical, where O-O scission occurs to form HPMF and (*)OH. In a few trajectories, we see HOOCH(2)OCHOOH recross back to (*)OOCH(2)OCH(2)OOH because the isomerization is endothermic, with only an 8 kcal/mol barrier to recrossing. Therefore, some inhibition of chain-branching may be due to recrossing. Second, trajectories run from the transition state leading to the direct decomposition of HPMF (an important source of the second (*)OH radical in chain branching) to HCO, (*)OH, and HC(=O)OH show that these products can recombine to form many other possible products. These products include CH(2)OO + HC(=O)OH, H(2)O + CO + HC(=O)OH, HC(=O)OH + HC(=O)OH, and HC

  20. Synthesis Laboratory for the U.S. Army Medical Research Institute of Infectious Diseases Selection Panel

    DTIC Science & Technology

    1988-01-19

    ANNUAL PROGRESS REPORT John A. Secrist III Cecil D. Kwong / Charles A. Krauth ’ Angela G. Ford Yajnanarayana H. R. Jois Deborah A. Carter...C. A. Krauth A. G. Ford H. R. Y. Jois D. A. Carter Analytical Services Dr. W. C. Coburn Dr. J. M. Riordan M. C. Kirk C. Richards R. T...7022 00361S 2.0 q /^ K ^^C=NNHCNHj *"S/ CH, 7023 003677 2.0 g S II C=NNHCNH, I 2 CH3 702> 003678 2.0 g NH "«1-®- OCH, HCIO„ 7037 003679

  1. Targeted Therapies for Myeloma and Metastatic Bone Cancers

    DTIC Science & Technology

    2006-02-01

    appropriately-sized particles from the biodegradable polymer polylactide -co-glycolide (PLGA). We developed two protocols for preparing narrowly-distributed...linker is to start with a bifunctional PEG and selectively attach to the respective ends either the bone-targeting ligand or a polylactide polymer. As...Polyethylene glycol - polylactide -co-galactide Block Copolymers 0 ,0. R",R"’. R.,R .... O° 01 O R",R" Catalyst 0 R",R"’. Product0 R’ = -•N• or -O-CH3 0 R",R

  2. Synthetic Beta-Lactam Antibiotics as a Selective Breast Cancer Cell Apoptosis Inducer: Significance in Breast Cancer Prevention and Treatment

    DTIC Science & Technology

    2007-03-01

    apoptosis in human breast cancer but not normal cells. To test this innovative hypothesis, we have performed the proposed experiments as reported below...H O OH3CO HY 20 O OCH3 N O SCH3 O ClO H N O HY16 The un-acylated bis-hydroxyl lactam, HY 17, was also prepared for testing . N O SCH3 HO...activities of novel β-lactams. In order to discover more potent β- lactams against cancer, we have tested numerous of β-lactams that were synthesized by

  3. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, J.V.

    1996-10-22

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  4. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, J.V.

    1996-01-23

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  5. [INFECTION OF BLOOD-SUCKING MOSQUITOES (DIPTERA: CULICIDAE) WITH DIROFILARIAE (SPIRURIDA, ONCHOCERCIDAE) IN THE TULA REGION].

    PubMed

    Bogacheva, A S; Ganushkina, L A; Lopatina, Yu V

    2016-01-01

    Blood-sucking mosquitoes (n = 2277) collected in Tula and its Region in 2013-2014 were examined using a PCR assay for dirofilariae. A total of 12 species from 4 genera (Culiseta, Aedes, Ochlerotatus [foreign character] Culex) out of 18 found mosquito species were infected with Dirofilaria immitis and D. repens. The proportion of the infected mosquitoes was 2.5% (D. immitis, 1.5%; D.repens, 1%). According to preliminary data, the most efficient Dirofilaria vectors, in the Tula Region may be Ae. vexans, Ae. geniculatus, Och. cantans, and Cx. pipiens.

  6. Characterization of supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

    PubMed

    Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

    2003-06-11

    Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

  7. Neurophysiological Bases of Event-Related Potentials.

    DTIC Science & Technology

    1986-08-08

    k-l. 0o Ln M -41-- X-4 CD0 -0 0 Gl) 1 4 V n .c D(Z -%x U) tr LJ W ~ -X Liu o O).ch w 4 - 4. r 0 -r glowJ 00r CL- * 4~% Ŕ W ’.4-4...Markey, S. P., Ebert, M. H., and Kopin , 1. J. A primate model of parkinsonism: selective destruction of dopaminergic neurons by N-methyl-4-phenyl-l,2,3,6

  8. Fabrication of biomimetic hydrophobic films with corrosion resistance on magnesium alloy by immersion process

    NASA Astrophysics Data System (ADS)

    Liu, Yan; Lu, Guolong; Liu, Jindan; Han, Zhiwu; Liu, Zhenning

    2013-01-01

    Biomimetic hydrophobic films of crystalline CeO2 were prepared on magnesium alloy by an immersion process with cerium nitrate solution and then modified with DTS (CH3(CH2)11Si(OCH3)3). The CeO2 films fabricated with 20-min immersion yield a water contact angle of 137.5 ± 2°, while 20-min DTS treatment on top of CeO2 can further enhance the water contact angle to 146.7 ± 2°. Then corrosion-resistant property of these prepared films against NaCl solution was investigated and elucidated using electrochemical measurements.

  9. New leads in speculative behavior

    NASA Astrophysics Data System (ADS)

    Kindler, A.; Bourgeois-Gironde, S.; Lefebvre, G.; Solomon, S.

    2017-02-01

    The Kiyotaki and Wright (1989) (henceforth KW) model of money emergence as a medium of exchange has been studied from various perspectives in recent papers. In the present work we propose a minimalistic model for the behavior of agents in the KW framework, which may either reproduce the theoretical predictions of Kiyotaki and Wright (1989) on the emerging Nash equilibria, or (less closely) the empirical results of Brown (1996), Duffy and Ochs (1999) and our own, introduced in a first part of the present paper. The main import is the systematic computer scanning of speculative monetary equilibria under drastic bounded rationality of agents, based on behavior previously observed in the lab.

  10. A zwitterionic carbanion frustrated by boranes--dihydrogen cleavage with weak Lewis acids via an "inverse" frustrated Lewis pair approach.

    PubMed

    Li, Hui; Aquino, Adelia J A; Cordes, David B; Hung-Low, Fernando; Hase, William L; Krempner, Clemens

    2013-10-30

    The synthesis, structural characterization, and acid-base chemistry of [C(SiMe2OCH2CH2OMe)3]Na (2), a sterically encumbered zwitterionic organosodium compound, is reported. 2 is a strong Brønsted base that forms frustrated Lewis pairs (FLPs) with a number of boron-containing Lewis acids ranging from weakly Lewis acidic aryl and alkyl boranes to various alkyl borates. These intermolecular FLPs readily cleave H2, which confirms that even poor Lewis acids can engage in FLP-mediated H2 cleavage provided that the present bulky base is of sufficiently high Brønsted basicity.

  11. Triaryl (Z)-olefins suitable for radiolabeling with iodine-124 or fluorine-18 radionuclides for positron emission tomography imaging of estrogen positive breast tumors.

    PubMed

    Abdellatif, Khaled R A; Velázquez, Carlos A; Huang, Zhangjian; Chowdhury, Morshed A; Knaus, Edward E

    2011-02-15

    A group of (Z)-1,2-diphenyl-1-[4-[2-(4-methylpiperazin-1-yl)ethoxy]phenyl]but-1-enes were synthesized using methodologies that will allow incorporation of a [(124)I]iodine substituent at the para-position of either the C-1 phenyl ring or the C-2 phenyl ring, or a [(18)F]OCH(2)CH(2)F substituent at the para-position of the C-2 phenyl ring. These [(124)I] and [(18)F] radiotracers are designed as potential radiopharmaceuticals to image estrogen positive breast tumors using positron emission tomography (PET).

  12. An effective route to fluorine containing asymmetric alpha-aminophosphonates using chiral Bronsted acid catalyst.

    PubMed

    Bhadury, Pinaki S; Zhang, Yuping; Zhang, Sha; Song, Baoan; Yang, Song; Hu, Deyu; Chen, Zhuo; Xue, Wei; Jin, Linhong

    2009-05-01

    Asymmetric addition of dialkyl phosphites (--CH2CH3, --CH2CH2CH3, --CH(CH3)2, --CH2(CH2)3CH3, --CH2CH2OCH3 and --CH2CH2OC2H5) induced by chiral organocatalyst e.g. (R)- and (S)-3,3'-[3,5-bis(trifluoromethyl)phenyl]2-1,1'-binaphthyl phosphate on fluorinated aldimines derived from cinnamaldehyde has been found effective to give new bioactive alpha-aminophosphonates in good yields (58-73%) and high enantiomeric excess (64.6%-90.6%) under mild conditions.

  13. Energy In Action: The Construction Of Physics Ideas In Multiple Modes

    NASA Astrophysics Data System (ADS)

    Close, Eleanor W.; Close, Hunter G.; McKagan, Sarah B.; Scherr, Rachel E.

    2010-10-01

    In a course organized around the development of diverse representations, no single mode of expression offers a complete picture of participants' understanding of the nature of energy. Instead, we argue, their understanding is actively constructed through the simultaneous use of a range of quite different kinds of representational resources (Goodwin, 2000; Hutchins, 1995; Ochs, Gonzales, & Jacoby, 1996), including not only words and prosody but also gestures, symbolic objects, participants moving their bodies in concert, and whatever other communicative modes the course invites them to use. Examples are provided from a teacher professional development course on energy.

  14. Multidimensional intermittency in hadronic collisions

    NASA Astrophysics Data System (ADS)

    Pan, Jicai; Hwa, Rudolph C.

    1992-12-01

    The study of intermittency in high-energy hadronic collisions by the Monte Carlo code ecco is extended to three-dimensional phase space. Strong intermittency is found in agreement with the data. Fluctuation in the impact parameter is responsible for the intermittency in lnpT, and the transverse-momentum conservation leads to negative intermittency slopes in the azimuthal angle φ. The Ochs-Wosiek plots are linear in all dimensions having universal slopes. An exponent ν=1.448 emerges to characterize multiparticle production in pp collisions. The properties of G moments are also examined, and the fractal dimensions determined.

  15. Multidimensional intermittency in hadronic collisions

    NASA Astrophysics Data System (ADS)

    Pan, J.; Hwa, R. C.

    1992-06-01

    The study of intermittency in high-energy hadronic collisions by the Monte Carlo code ECCO is extended to 3-dimensional phase space. Strong intermittency is found in agreement with the data. Fluctuation in the impact parameter is responsible for the intermittency in 1np(sub T), and the transverse-momentum conservation leads to negative intermittency slopes in the azimuthal angle (phi). The Ochs-Wosiek plots are linear in all dimensions having universal slopes. An exponent nu = 1.448 emerges to characterize multiparticle production in pp collisions. The properties of G moments are also examined, and the fractal dimensions determined.

  16. Outer scale of atmospheric turbulence

    NASA Astrophysics Data System (ADS)

    Lukin, Vladimir P.

    2005-10-01

    In the early 70's, the scientists in Italy (A.Consortini, M.Bertolotti, L.Ronchi), USA (R.Buser, Ochs, S.Clifford) and USSR (V.Pokasov, V.Lukin) almost simultaneously discovered the phenomenon of deviation from the power law and the effect of saturation for the structure phase function. During a period of 35 years we have performed successively the investigations of the effect of low-frequency spectral range of atmospheric turbulence on the optical characteristics. The influence of the turbulence models as well as a outer scale of turbulence on the characteristics of telescopes and systems of laser beam formations has been determined too.

  17. Determination of the Minimum Energy Conformations of Benzyl Alcohol and 2-Phenethyl Alcohol

    DTIC Science & Technology

    1989-12-14

    ethylbenzyl alcohol (4-EtBA), 2 - methylbenzyl alcohol (2 -MeBA), 3- methylbenzyl alcohol (3-MeBA), 2 -PEA, 2-(o-methyl phenyl)-ethanol (2-(o-CH3)-PEA...conformers in the ground state. 3. 3- Methylbenzyl alcohol and 3-Fluorobenzyl alcohol The TOFMS of jet-cooled 3-MeBA is presented in Fig. 3. As found...these peaks are thus exactly the same as those for BA. This molecule has a single stable conformer, just as BA. 4. 2- Methylbenzyl alcohol The mass

  18. Phosphazenes with Olefinic Side Groups: Proton Abstraction Reactions of Fluoroalkoxy Derivatives.

    DTIC Science & Technology

    1982-06-24

    OPh) (OC(Li)=CF2) 13 and [NP(OC(Li)CF2)2]3 1 respectively. These species are stable in solution at -78*C, but react with electrophiles such as 2...an -OCH2CF3 side group to generate an -OC(M)-CF2 unit. Subsequent treatment with an electrophile was designed to yield an -OC(R)-CF2 side group...resonances for the fluorine atoms in 2 and 5 appeared as multiplets due to the slight differences in chemical shift between the cis and trans

  19. Adsorption of Trimethyl Phosphite on H-KA, H-NaA, H-CaA and H-NaX Zeolites: an IR Study

    NASA Astrophysics Data System (ADS)

    Çiçek, E.; Bardakçı, B.; Ucun, F.; Bahçeli, S.

    2003-06-01

    Infrared spectroscopy has been used in adsorption studies of trimethyl phosphite (TMP) on the hydrogen (H) form of the A-type and 13X zeolites. Infrared spectra of H-zeolites, except H-KA, show that TMP reacts rapidly with silanol hydroxyls on their surfaces and gives rise to form product molecules such as SiOCH3 and liquid dimethyl phosphite. The unaccomplished adsorption on the H-KA zeolite has been attributed to the occurence of stable KOH hydroxyls with not-exchanged K cations instead of SiOH hydroxyls on this zeolite.

  20. Film deposition and UV curing process impact on ultralow-k dielectric for high performance Cu interconnects

    NASA Astrophysics Data System (ADS)

    Gu, Xun; Deng, Hao; Tong, Zheyuan; Jing, Xuezhen

    2017-07-01

    Ultralow-k (ULK) film deposition and UV curing process were studied to explore the effects on the mechanical, electrical and chemical properties of ULK dielectrics. UV curing process plays an important role to enhance the Young’s modulus (mechanical performance) by increasing the formation of -Si-O-Si- cross-linking, and ULK film deposition with low film shrinkage ratio can form a robust porous SiOCH to avoid following integration process-induced damage on ULK dielectrics and also improve the device reliability performance significantly.

  1. [2]pseudorotaxane formation with N-benzylanilinium axles and 24-crown-8 ether wheels.

    PubMed

    Loeb, Stephen J; Tiburcio, Jorge; Vella, Sarah J

    2005-10-27

    [reaction: see text] As a hybrid of the N,N-dibenzylammonium and 1,2-bis(pyridinium)ethane axles, various N-benzylanilinium cations were investigated as suitable axles for the formation of [2]pseudorotaxanes with the 24-membered crown ethers 24C8 and DB24C8. The effect of electron-donating OCH(3) and electron-withdrawing CF(3) groups on both the anilinium and benzyl aromatic rings was studied. Formation constants and structural details were compared to the [2]pseudorotaxanes formed by the two aforementioned dibenzylammonium and 1,2-bis(pyridinium)ethane axles.

  2. Extending Phrase-Based Decoding with a Dependency-Based Reordering Model

    DTIC Science & Technology

    2009-11-01

    w3 w4 w5 (a) IBM Models (Brown et al., 1990, 1993) w1 w2 w3 w4 w5 (b) Yamada and Knight (2001, 2002) w1w2 w3 w4w5 (c) Pharaoh (Och et al., 1999...phrases Distortion models BLEU Notes Pharaoh Dep. Lex. Dep. Czech Arabic (i) Pharaoh phrases X 33.28 45.28 Standard Pharaoh (ii) Random phrases X 20.53...29.75 Randomly crippled Pharaoh (iii) Licensed phrases X 32.54 28.02 Systematically crippled Pharaoh (iv) X 24.13 24.50 Attempts at improvement(v) X X

  3. Effects of deuteration of the methyl and phenyl hydrogens on the rotational spectrum of anisole-water

    NASA Astrophysics Data System (ADS)

    Giuliano, Barbara M.; Melandri, Sonia; Caminati, Walther

    2017-07-01

    The role of non-covalent interactions in determining the structure of the 1:1 anisole-water molecular complex has been investigated by the analysis of the rotational spectra of the complex formed by the C6H5OCD3 and C6D5OCH3 deuterated species of anisole recorded with pulsed jet Fourier transform microwave spectroscopy. The deuteration of the methyl and phenyl hydrogens does not affect the structure and the internal dynamics of the complex, differently from the deuteration of the water moiety, which leads to large isotopic effects (Giuliano et al., 2005).

  4. Structure-spectroscopic property relationships in a series of platinum acetylides

    NASA Astrophysics Data System (ADS)

    Cooper, Thomas M.; Haley, Joy E.; Krein, Douglas M.; Burke, Aaron R.; Slagle, Jonathan E.

    2016-09-01

    In order to understand electronic and conformational effects on structure-spectroscopic property relationships in platinum acetylides, we synthesized a model series of chromophores trans-Pt(PBu3)2(C-CPhenyl-X)2, where X = NH2, OCH3, diphenylamino, t-Bu, methyl, H, F, benzothiazole, trifluoromethyl, CN and nitro. We collected linear spectra, including ground state absorption, phosphorescence and phosphorescence excitation spectra. We also performed DFT and TDDFT calculations on the ground and excited state properties of these compounds. The calculations and experimental data show the excited state properties are a function of the electronic properties of the substituents and the molecular conformation.

  5. Spectrofluorimetric study of the binding of codeine to nucleic acids

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Huang, Wei; Su, Liang; Dong, Zijia; Zhang, Shuai

    2009-06-01

    The characteristics of the interaction between codeine (CD) and nucleic acids were studied by ultraviolet-visible spectra and fluorescent spectra. It shows that there is a powerful ability in nucleic acids to quench the fluorescence intensity of codeine. The fluorescence quenching data were analyzed according to Stern-Volmer equation and Förster's nonradiative energy transfer mechanism. Thus the binding constant and the thermodynamic parameters between codeine and nucleic acids were obtained. The results show that codeine interacts with nucleic acids in a mode of groove binding and -OCH 3 of the codeine molecular combines with the groove of nucleic acids through hydrogen bond or van der Waals force.

  6. 1-(2-Thienyl)-2-phenylethylamines as potential non-stimulant anorectics.

    PubMed

    Mrongovius, R I; Ghosh, P; Bolt, A G; Ternai, B

    1981-01-01

    A series of 1-(2-thienyl)-2-phenylethylamines was synthesized and tested for anorectic and motor activity effects in rats. Phenyl ring substituents included Cl, Br, F, CF3, CH3, OCH3, and NO2; amino group substituents included alkyl, benzyl and acetyl groups. About half of the compounds produced significant anorexia; only one of these active anorectics increased motor activity. The three most potent non-stimulant anorectics were: 1-(2-thienyl)-2-(4-chlorophenyl)ethylamine, its N-isopropyl analogue, and N-isopropyl-1-(2-thienyl)-2-(4-fluorophenyl)ethylamine.

  7. [Oligonucleotide analogues bearing an acyclonucleoside linked by an internucleotide amide bond].

    PubMed

    Kochetkova, S V; Fillipova, E A; Kolganova, N A; Timofeev, E N; Florent'ev, V L

    2008-01-01

    Oligonucleotide analogues bearing an acyclocytidine linked to thymidine by an amide (3'-O-CH2-CO-N-5') bond were synthesized. Melting curves of duplexes formed by modified oligonucleotides and complementary natural oligomers were obtained and thermodynamic parameters of their formation were measured. Replacement of dCpT by a modified dinucleotide only moderately decreased the melting temperature of these modified duplexes in comparison with unmodified duplexes containing complementary natural bases. CD spectra of modified duplexes were studied, and the duplex spatial structures are discussed. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also http://www.maik.ru.

  8. Syntheses of 4,6'-epoxymorphinan derivatives and their pharmacologies.

    PubMed

    Nemoto, Toru; Fujii, Hideaki; Narita, Minoru; Miyoshi, Kan; Nakamura, Atsushi; Suzuki, Tsutomu; Nagase, Hiroshi

    2008-04-15

    A modification of the message site in the skeleton of naltrexone was carried out to improve the potency and selectivity of the compound for an opioid receptor subtype. In the course of conversion, we synthesized 7-membered ring ether derivatives, which had an inserted OCH(2) group between 4- and 6-positions of morphinan skeleton. One of the 7-membered ring ether derivatives possessed more potent antagonistic activity than naltrexone for the mu opioid receptor. Another compound possessing 17-methyl group derived from noroxycodone may be a mu opioid receptor partial agonist and showed analgesic activity. We are currently examining the subtype selectivity of these compounds.

  9. Increasing the activity and enantioselectivity of lipases by sol-gel immobilization: further advancements of practical interest

    NASA Astrophysics Data System (ADS)

    Tielmann, Patrick; Kierkels, Hans; Zonta, Albin; Ilie, Adriana; Reetz, Manfred T.

    2014-05-01

    The entrapment of lipases in hydrophobic silicate matrices formed by sol-gel mediated hydrolysis of RSi(OCH3)3/Si(OCH3)4 as originally reported in 1996 has been improved over the years by a number of modifications. In the production of second-generation sol-gel lipase immobilizates, a variety of additives during the sol-gel process leads to increased activity and enhanced stereoselectivity in esterifying kinetic resolution. Recent advances in this type of lipase immobilization are reviewed here, in addition to new results regarding the sol-gel entrapment of the lipase from Burkholderia cepacia. It constitutes an excellent heterogeneous biocatalyst in the acylating kinetic resolution of two synthetically and industrially important chiral alcohols, rac-sulcatol and rac-trans-2-methoxycyclohexanol. The observation that the catalyst can be used 10 times in recycling experiments without losing its significant activity or enantioselectivity demonstrates the practical viability of the sol-gel approach.The entrapment of lipases in hydrophobic silicate matrices formed by sol-gel mediated hydrolysis of RSi(OCH3)3/Si(OCH3)4 as originally reported in 1996 has been improved over the years by a number of modifications. In the production of second-generation sol-gel lipase immobilizates, a variety of additives during the sol-gel process leads to increased activity and enhanced stereoselectivity in esterifying kinetic resolution. Recent advances in this type of lipase immobilization are reviewed here, in addition to new results regarding the sol-gel entrapment of the lipase from Burkholderia cepacia. It constitutes an excellent heterogeneous biocatalyst in the acylating kinetic resolution of two synthetically and industrially important chiral alcohols, rac-sulcatol and rac-trans-2-methoxycyclohexanol. The observation that the catalyst can be used 10 times in recycling experiments without losing its significant activity or enantioselectivity demonstrates the practical viability of

  10. Structure and reactions of cation-radicals of esters in freon matrices

    SciTech Connect

    Belevskii, V.N.; Belopushkin, S.I.; Fel'dman, V.I.

    1987-11-01

    In CFCl/sub 3/ matrices the cation-radicals of methyl and ethyl formates, formed in ..gamma..-irradiated solutions, at 77 K efficiently undergo intramolecular H atom transfer to form the secondary cation-radicals HC(OH)OCH/sub 2/CH/sub 2/ and DC(OH)OCD/sub 2/CH/sub 2/. This process does not occur in the deuteroformate cation-radical DCOOCH/sub 2/CD/sub 3//sup +./, which is observed in the ESR spectra in different conformations, depending on the temperature. Ion-molecule reactions involving cation-radicals are indicated

  11. Infrared spectroscopic study of the rotation of chemisorbed methoxy species on an alumina surface

    SciTech Connect

    Beebe, T.P. Jr.; Crowell, J.E.; Yates, J.T. Jr. )

    1990-04-15

    We present experimental and calculated vibration--rotation spectra as a function of temperature for the methoxy species (--OCH{sub 3} and --OCD{sub 3}) chemisorbed on an alumina surface. The axis of rotation is the C--O bond axis. The model for our calculations is that of free rotation, and we describe the methods employed here in full detail. The qualitative agreement between the calculated and experimental spectra suggests that the adsorbed methoxy species is undergoing free rotational motion about the C--O bond axis.

  12. High Performance Composites Based on Polyurethanes Reinforced with Polydiacetylenes

    DTIC Science & Technology

    1989-04-04

    used in which miscible blends of polyester diol pre-polymers and a monomeric, diacetylene diol were reacted with a diisocyanate in a single-step...Purification and Characterisation 15 of Reactants 4,4’ -Methylenediphenylene diisocyanate MDI 16 Polyoxypropylene diols PPGI000 and PPG400 16 2,4...liquid variant (M340) of 4,4’-methylenediphenylene diisocyanate MDI (v). 3 HO CH3 CH20H > CHfCCH2 CHnOCH C2H5 --CH2 CH OCN Q CH2 Q NCO HO CH2 H (ii) (v

  13. Synthesis of homoleptic barium alkoxides and aryloxides and their reactions with Al(CH(3))(3): a convenient route to heterometallic species.

    PubMed

    Utko, Józef; Szafert, Sławomir; Jerzykiewicz, Lucjan B; Sobota, Piotr

    2005-07-25

    Reactions of metallic Ba with benzofuranol (dbbfoH) or diethylene glycol give homoleptic and homonuclear complexes Ba(dbbfo)(2)(dbbfoH)(2).3dbbfoH and Ba{O(CH(2)CH(2)O)(2)}{O(CH(2)CH(2)OH)(2)}(2) (60-89%). Both compounds and formerly described Ba{O(CH(2)CH(2)O)(2)Me}(2) react with Al(CH(3))(3) to yield trinuclear heterobimetallic low-coordinated barium compounds with structure and geometry depending on the reaction stoichiometry and crystallization procedure.

  14. Mass analyzed threshold ionization spectroscopy of p-methylanisole cation and the substitution effect

    NASA Astrophysics Data System (ADS)

    Huang, Jiangou; Li, Changyong; Tzeng, Wen Bih

    2005-10-01

    The adiabatic ionization energy of p-methylanisole is measured to be 63 972 ± 5 cm -1, which is red-shifted with respect to those of anisole and toluene. This indicates that the interaction of either CH 3 or OCH 3 group with the ring is stronger in the cationic D 0 state than that in the neutral S 0 state. Most of the observed MATI bands result from in-plane ring vibrations. The frequencies of vibrations 9b, 6a, and 1 of the p-methylanisole cation are found to be 407, 515, and 811 cm -1, respectively.

  15. Polymerization of styrene with cyclopentadienyl nickel complex/methylaluminoxane

    NASA Astrophysics Data System (ADS)

    Yu, Dongping; Zhang, Danfeng

    2017-09-01

    Polystyrene was synthesized by Cp(CH2CH2OCH3)NiCl(PPh3) in the presence of methylaluminoxane (MAO). This complex displayed a very high activity for styrene polymerization up to 107 g.mol-1Nih-1. 76.6% styrene was converted to polystyrene (PS) with an average molecular (Mn) of 1.13×105 at 50 °C in 30 min. The structure of the obtained polymer was characterized by 1H NMR and FT-IR.

  16. Electrospray ionization tandem mass spectrometric study of protonated and alkali- cationized α/ε-hybrid peptides: differentiation of a pair of dipeptide positional isomers.

    PubMed

    Ramesh Babu, A; Raju, G; Purna Chander, C; Shoban Babu, B; Srinivas, R; Sharma, G V M

    2016-01-01

    A new class of Boc-N-protected hybrid peptides derived from L- Ala and ε(6)-Caa (L-Ala = L-Alanine, Caa = C-linked carboamino acid derived from D-xylose) have been studied by positive ion electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS). MS(n) spectra of protonated and alkali-cationized hybrid peptides produce characteristic fragmentation involving the peptide backbone, the tert-butyloxycarbonyl (Boc) group, and the side chain. The dipeptide positional isomers are differentiated by the collision-induced dissociation (CID) of the protonated and alkali-cationized peptides. The CID of [M + H](+) ion of Boc-NH-L-Ala-ε-Caa- OCH3 (1) shows a prominent [M + H - C4H8](+) ion, which is totally absent for its positional isomer Boc-NH-ε-Caa-L-Ala-OCH3 (6), which instead shows significant loss of t-butanol. The formation of the [M + Cat - C4H8](+) ion is totally absent and [M + Cat - Boc + H](+) is prominent in the CID of the [M + Cat](+) ion of Boc-NH-L-Ala-ε-Caa- OCH3 (1), whereas the former is highly abundant and the latter is of low abundance for its positional isomer Boc-NH-ε-Caa-L-Ala-OCH3 (6). It is observed that 'b' ions are abundant when oxazolone structures are formed through a five-membered cyclic transition state in tetra-, penta-, and hexapeptides and the cyclization process for larger 'b' ions led to an insignificant abundance. However, the significant 'b' ion is formed in ε,α-dipeptide, which may have a seven-membered substituted 2-oxoazepanium ion structure. The MS(n) spectra of [M + Cat - Boc + H](+) ions of these peptides are found to be significantly different to those of [M + H - Boc + H](+) ions. The CID spectra of [M + Cat - Boc + H](+) ions of peptide acids containing L-Ala at the C-terminus show an abundant N-terminal rearrangement ion, [b(n) + 17 + Cat](+), which is absent for the peptide acids containing ε-Caa at the C-terminus. Thus, the results of these hybrid peptides

  17. Chapter 25 First-Principles Investigation of Dimethyl Ether Steam Reforming

    NASA Astrophysics Data System (ADS)

    Fukushima, Kimichika

    This paper reports the investigation of dimethyl ether (DME) steam reforming and related processes. The study uses the X[alpha] molecular orbital theory, which has been successfully applied to analyze material properties. It was found that, when H2O approaches Al on a surface of Si oxides (and pure Al2O3), charge transfer between H2O and the surface destabilizes the H2O. Approach of the destabilized H to a CH3OCH3 molecule then produces CH3OH. Finally, injection of CO2, by-produced in the reforming, to coal seam was shown to increase the CH4 production by substitution.

  18. New sandwich-type lanthanide complexes based on closed-macrocyclic Schiff base and phthalocyanine molecules.

    PubMed

    Gao, Feng; Feng, Xiaowan; Yang, Liu; Chen, Xiaoyu

    2016-04-25

    Two new sandwich-type lanthanide complexes with the general formula [(Pc)2Ln3(L)(OAc)(OCH3)2] (Ln(3+) = Dy(3+) () and Er(3+) ()) were successfully synthesized and structurally characterized based on closed-macrocyclic Schiff base and phthalocyanine molecules. The magnetic properties and structure-property relationship in this multi-decker system were investigated. Interestingly, the corresponding dysprosium complex shows typical single-molecule magnetic behavior with ferromagnetic dipole-dipole interactions and the slow relaxation of magnetization.

  19. Ring-expansion reaction of oximes with aluminum reductants.

    PubMed

    Cho, Hidetsura; Iwama, Yusuke; Mitsuhashi, Nakako; Sugimoto, Kenji; Okano, Kentaro; Tokuyama, Hidetoshi

    2012-06-14

    The ring-expansion reactions of heterocyclic ketoximes and carbocyclic ketoximes with several reductants such as AlHCl2, AlH3 (alane), LiAlH4, LiAlH(OtBu)3, and (MeOCH2CH2O)2AlH2Na (Red-Al) were examined. Among reductants, AlHCl2 (LiAlH4:AlCl3 = 1:3) in cyclopentyl methyl ether (CPME) has been found to be a suitable reagent for the reaction, and the rearranged cyclic secondary amines were obtained in good to excellent yields.

  20. Synthesis of Peptides Containing C-Terminal Methyl Esters Using Trityl Side-Chain Anchoring: Application to the Synthesis of a-Factor and a-Factor Analogs

    PubMed Central

    Diaz-Rodriguez, Veronica; Mullen, Daniel G.; Ganusova, Elena; Becker, Jeffrey M.; Distefano, Mark D.

    2012-01-01

    A new cysteine anchoring method was developed for the synthesis of peptides containing C-terminal cysteine methyl esters. This method consists of attachment of Fmoc-Cys-OCH3 to either 2-ClTrt-Cl or Trt-Cl resins (via the side-chain thiol) followed by preparation of the desired peptide using Fmoc-based SPPS. We applied this method to the synthesis of the mating pheromone a-factor and a 5-FAM labeled a-factor analog. The peptides were obtained with high yield and purity and were shown to be bioactive in a growth arrest assay. PMID:23121562

  1. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  2. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  3. Acceleration of the imaginary time method for spectrally computing the stationary states of Gross-Pitaevskii equations

    NASA Astrophysics Data System (ADS)

    Antoine, Xavier; Besse, Christophe; Duboscq, Romain; Rispoli, Vittorio

    2017-10-01

    The aim of this paper is to propose a simple accelerated spectral gradient flow formulation for solving the Gross-Pitaevskii Equation (GPE) when computing the stationary states of Bose-Einstein Condensates. The new algorithm, based on the recent iPiano minimization algorithm (Ochs et al., 2014), converges three to four times faster than the standard implicit gradient scheme. To support the method, we provide a complete numerical study for 1d-2d-3d GPEs, including rotation and dipolar terms.

  4. Synthesis of peptides containing C-terminal methyl esters using trityl side-chain anchoring: application to the synthesis of a-factor and a-factor analogs.

    PubMed

    Diaz-Rodriguez, Veronica; Mullen, Daniel G; Ganusova, Elena; Becker, Jeffrey M; Distefano, Mark D

    2012-11-16

    A new cysteine anchoring method was developed for the synthesis of peptides containing C-terminal cysteine methyl esters. This method consists of attachment of Fmoc-Cys-OCH(3) to either 2-ClTrt-Cl or Trt-Cl resins (via the side-chain thiol) followed by preparation of the desired peptide using Fmoc-based SPPS. We applied this method to the synthesis of the mating pheromone a-factor and a 5-FAM labeled a-factor analog. The peptides were obtained with high yield and purity and were shown to be bioactive in a growth arrest assay.

  5. Vinyloxychloro-cyclotriphosphazenes.

    DTIC Science & Technology

    1982-12-06

    STATEMENT (of this Report) Approved for public release and sale; its distribution is unlimited. 17 . DISTRIBUTION STATEMENT (of the abstract entered In...trans): 4.6 (m), JH-H (trans): 13.6, JH-H (gem)=2.2, 3JPH n 2.0; 6-P-0-CH-CH 2 (cis)-4.2 (m), JH-H (cis)-5.9, JH-H (gem) - 2.2, 4pH ’ 1.8; 6 -P(OCH-CH...920 (m, PN), 870 (m, PN), 810 (m), 770 (m), 695 (m). There are two possible routes of reaction for anambident enolate anion leading 17 to

  6. Performance Evaluation of Potential Fuel System Icing Inhibitors in Aviation Jet Fuel Using the US Navy Aircraft Fuel System Icing Simulator

    DTIC Science & Technology

    1997-05-29

    candidate. Empirical formula: CgH14°4. o HC II 21’O~CH3 HC-CH3 HL....Oy CH32 I o 5 NAVAIRWARCENACDIVTRENTON-LR-PPE-97-3 (20) 2-Methyl-l,3- Propanediol ...friendly FSII candidate. Empirical formula: C4H1002. H2C-OH --/ HC- CH3 / H2C-OH (21) A mixture ofthree components (8% 2-Methy1-1,3- Propanediol ; 48% 3...Navy/U.S. Air ForceFSn development project; an environmentally friendly FSII candidate. 2-Methyl-l,3- Propanediol 3-Hydroxy-2-MethylPropyl Acetate + o

  7. Cyclodextrin Complexes of Reduced Bromonoscapine in Guar Gum Microspheres Enhance Colonic Drug Delivery

    PubMed Central

    2015-01-01

    Here, we report improved solubility and enhanced colonic delivery of reduced bromonoscapine (Red-Br-Nos), a cyclic ether brominated analogue of noscapine, upon encapsulation of its cyclodextrin (CD) complexes in bioresponsive guar gum microspheres (GGM). Phase–solubility analysis suggested that Red-Br-Nos complexed with β-CD and methyl-β-CD in a 1:1 stoichiometry, with a stability constant (Kc) of 2.29 × 103 M–1 and 4.27 × 103 M–1. Fourier transforms infrared spectroscopy indicated entrance of an O–CH2 or OCH3–C6H4–OCH3 moiety of Red-Br-Nos in the β-CD or methyl-β-CD cavity. Furthermore, the cage complex of Red-Br-Nos with β-CD and methyl-β-CD was validated by several spectral techniques. Rotating frame Overhauser enhancement spectroscopy revealed that the Ha proton of the OCH3–C6H4–OCH3 moiety was closer to the H5 proton of β-CD and the H3 proton of the methyl-β-CD cavity. The solubility of Red-Br-Nos in phosphate buffer saline (PBS, pH ∼ 7.4) was improved by ∼10.7-fold and ∼21.2-fold when mixed with β-CD and methyl-β-CD, respectively. This increase in solubility led to a favorable decline in the IC50 by ∼2-fold and ∼3-fold for Red-Br-Nos−β-CD-GGM and Red-Br-Nos–methyl-β-CD-GGM formulations respectively, compared to free Red-Br-Nos−β-CD and Red-Br-Nos–methyl-β-CD in human colon HT-29 cells. GGM-bearing drug complex formulations were found to be highly cytotoxic to the HT-29 cell line and further effective with simultaneous continuous release of Red-Br-Nos from microspheres. This is the first study to showing the preparation of drug-complex loaded GGMS for colon delivery of Red-Br-Nos that warrants preclinical assessment for the effective management of colon cancer. PMID:25350222

  8. Alkylation of urinary guanine in mice by the organophosphorus insecticide tetrachlorvinphos.

    PubMed

    Zayed, S M; Mostafa, I Y; Hegazi, B

    1984-06-01

    The methylating capability of tetrachlorvinphos on urinary guanine in mice has been investigated using an insecticide labeled at both O-CH3 groups. Following intraperitoneal administration of the 14C-labeled insecticide to mice, about 0.57% of the radioactivity in the O- to 24-hr samples was associated with the purine fraction. The amount of [7-14C]methylguanine in 0- to 48-hr urine samples, estimated as fraction of applied dose, was 26-31 X 10(-5). The results obtained indicate possible chemical alkylation of urinary guanine. On the other hand, a considerable portion of radioactivity is probably incorporated via the C-1 pool.

  9. A Theoretical Study of Methanol Oxidation Catalyzed by Isolated Vanadia Clusters Supported on the (101) Surface of Anatase

    SciTech Connect

    Shapovalov, Vladimir; Fievez, Tim; Bell, Alexis T.

    2012-08-13

    A theoretical model has been developed for describing isolated vanadate species dispersed on the (101) surface of anatase that takes into account the equilibration of the supported species with gas-phase oxygen. The lowest energy of the combined solid and gas phases identifies the VOx species with the optimal structure and composition. This model of VOx species supported on the surface of anatase is then used to analyze the reaction path for methanol oxidation to formaldehyde. The chemisorption of methanol is found to proceed preferentially by addition across a V-O-Ti bond to form V-OCH3 and Ti-OH species. The rate-limiting step for the formation of formaldehyde takes place via the transfer of a hydrogen atom from V-OCH3 bound to an oxygen atom bridging two Ti atoms, i.e., a Ti-O-Ti group located adjacent to the supported vanadate species. This step is found to have the lowest apparent activation energy of all pathways explored for the formation of formaldehyde.

  10. Design of peptides with α,β-dehydro-residues: syntheses, crystal structures and molecular conformations of two ΔPhe-Trp containing peptides

    NASA Astrophysics Data System (ADS)

    Vijayaraghavan, R.; Makker, J.; Kumar, P.; Dey, S.; Singh, T. P.

    2003-06-01

    The ΔPhe-Trp is a newly designed moiety that was found inducing a unique conformation in peptides. The peptides Boc-L-Val-ΔPhe-L-Trp-OCH 3 (I) and Boc-L-Leu-ΔPhe-L-Trp-OCH 3 (II) were synthesized by azlactone method in solution phase. The peptide (I) was crystallized from its solution in ethanol-water mixture in orthorhombic space group P2 12 12 1 with a=10.663(3) Å, b=11.204(3) Å, c=26.516(10) Å and peptide (II) was crystallized from its solution in acetone in a monoclinic space group P2 1 with a=9.354(1)Å, b=11.218(4)Å, c=15.633(1)Å and β=101.83(1)°. The structures were determined by direct methods. Peptide (I) was refined to an R value of 0.059 for 1554 observed reflections [ I≥2 σ (I)] and peptide (II) was refined to an R value of 0.043 for 2920 observed reflections [ I≥2 σ (I)]. The structures of peptides (I) and (II) were found to be identical. They formed an unusual type VIa β-turn conformation which is observed for the first time with a ΔPhe residue at ( i+2) position indicating a unique influence of ΔPhe-Trp moiety in inducing a reproducible new structure in peptides.

  11. Separating Chemical and Excluded Volume Interactions of Polyethylene Glycols with Native Proteins: Comparison with PEG Effects on DNA Helix Formation

    PubMed Central

    Shkel, Irina A.; Knowles, Ben; Record, M. Thomas

    2015-01-01

    Small and large PEGs greatly increase chemical potentials of globular proteins (μ2), thereby favoring precipitation, crystallization, and protein-protein interactions that reduce water-accessible protein surface and/or protein-PEG excluded volume. To determine individual contributions of PEG-protein chemical and excluded volume interactions to μ2 as functions of PEG molality m3, we analyze published chemical potential increments μ23 = dμ2/dm3 quantifying unfavorable interactions of PEG (PEG200-PEG6000) with BSA and lysozyme. For both proteins, μ23 increases approximately linearly with the number of PEG residues (N3). A 1 molal increase in concentration of PEG -CH2OCH2- groups, for any chain-length PEG, increases μBSA by ~2.7 kcal/mol and μlysozyme by ~1.0 kcal/mol. These values are similar to predicted chemical interactions of PEG -CH2OCH2- groups with these protein components (BSA ~3.3 kcal/mol, lysozyme ~0.7 kcal/mol), dominated by unfavorable interactions with amide and carboxylate oxygens and counterions. While these chemical effects should be dominant for small PEGs, larger PEGS are expected to exhibit unfavorable excluded volume interactions and reduced chemical interactions because of shielding of PEG residues in PEG flexible coils. We deduce that these excluded volume and chemical shielding contributions largely compensate, explaining why the dependence of μ23 on N3 is similar for both small and large PEGs. PMID:25924886

  12. Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

    SciTech Connect

    Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil; Zimmt, Matthew B.

    2012-12-01

    Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP contains carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.

  13. One-pot Solvothermal Synthesis of Well-ordered Layered Sodium Aluminoalcoholate Complex: A Useful Precursor for the Preparation of Porous Al2O3 Particles†

    PubMed Central

    Li, Xiansen; Michaelis, Vladimir K.; Ong, Ta-Chung; Smith, Stacey J.; McKay, Ian; Müller, Peter; Griffin, Robert G.; Wang, Evelyn N.

    2014-01-01

    One-pot solvothermal synthesis of a robust tetranuclear sodium hexakis(glycolato)tris(methanolato)aluminate complex Na3[Al4(OCH3)3(OCH2CH2O)6] via a modified yet rigorous base-catalyzed transesterification mechanism is presented here. Single crystal X-ray diffraction (SCXRD) studies indicate that this unique Al complex contains three penta-coordinate Al3+ ions, each bound to two bidentate ethylene glycolate chelators and one monodentate methanolate ligand. The remaining fourth Al3+ ion is octahedrally coordinated to one oxygen atom from each of the six surrounding glycolate chelators, effectively stitching the three penta-coordinate Al moieties together into a novel tetranuclear Al complex. This aluminate complex is periodically self-assembled into well-ordered layers normal to the [110] axis with the intra-/inter-layer bindings involving extensive ionic bonds from the three charge-counterbalancing Na+ cations rather than the more typical hydrogen bonding interactions as a result of the fewer free hydroxyl groups present in its structure. It can also serve as a valuable precursor toward the facile synthesis of high-surface-area alumina powders using a very efficient rapid pyrolysis technique. PMID:24817826

  14. Convenient synthesis and characterization of silane-capped polysiloles for the fabrication of luminescent OLED.

    PubMed

    Kim, Myoung-Hee; Kim, So-Yeun; Kim, Bo-Hye; Woo, Hee-Gweon; Park, Sook-Hyun; Kim, You-Jeong

    2008-09-01

    Catalytic dehydropolymerization and subsequent silane-capping with R2SiHCI (R = Ph, Me) of 1,1-dihydrotetraphenylsilole (1) using various inorganic hydrides produces electroluminescent silane-capped polysiloles (2) in high yield. The polymerization yield and molecular weight increase in the order LiB[CH(CH3)C2H5]3H < NaB[CH(CH3)C2H5]3H < KB[CH(CH3)C2H5]3H. The molecular weights increase in the order Na[H2Al(OCH2CH2OCH3)2] < KB[CH(CH3)C2H5]3H < LiB(C2H5)3H. The silane-capped polysiloles 2 emit at 521 nm and are electroluminescent at 522 nm. The fluorescence quantum yield of 2 in toluene is (1.67 +/- 0.31) x 10(-2). The emission color is green and the maximum brightness of the device is 2900 cd/m2 with a luminous efficiency of 0.69 lm/W. The substituent type of silyl end group showed no appreciable effect on the luminescent properties of polysilole backbone. Thus, the silane-capped polysiloles are found to be a good material for OLED fabrication. A possible mechanism for the formation of 2 was suggested.

  15. Non-strinking siloxane polymers

    DOEpatents

    Loy, Douglas A.; Rahimian, Kamyar

    2001-01-01

    Cross-linked polymers formed by ring-opening polymerization of a precursor monomer of the general formula R[CH.sub.2 CH(Si(CH.sub.3).sub.2).sub.2 O].sub.2, where R is a phenyl group or an alkyl group having at least two carbon atoms. A cross-linked polymer is synthesized by mixing the monomer with a co-monomer of the general formula CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O in the presence of an anionic base to form a cross-linked polymer of recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2 [CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O].sub.n, where R.sup.2 is hydrogen, phenyl, ethyl, propyl or butyl. If the precursor monomer is a liquid, the polymer can be directly synthesized in the presence of an anionic base to a cross-linked polymer containing recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2. The polymers have approximately less than 1% porosity and are thermally stable at temperatures up to approximately 500.degree. C. The conversion to the cross-linked polymer occurs by ring opening polymerization and results in shrinkage of less than approximately 5% by volume.

  16. T helper type 2-polarized invariant natural killer T cells reduce disease severity in acute intra-abdominal sepsis

    PubMed Central

    Anantha, R V; Mazzuca, D M; Xu, S X; Porcelli, S A; Fraser, D D; Martin, C M; Welch, I; Mele, T; Haeryfar, S M M; McCormick, J K

    2014-01-01

    Sepsis is characterized by a severe systemic inflammatory response to infection that is associated with high morbidity and mortality despite optimal care. Invariant natural killer T (iNK T) cells are potent regulatory lymphocytes that can produce pro- and/or anti-inflammatory cytokines, thus shaping the course and nature of immune responses; however, little is known about their role in sepsis. We demonstrate here that patients with sepsis/severe sepsis have significantly elevated proportions of iNK T cells in their peripheral blood (as a percentage of their circulating T cells) compared to non-septic patients. We therefore investigated the role of iNK T cells in a mouse model of intra-abdominal sepsis (IAS). Our data show that iNK T cells are pathogenic in IAS, and that T helper type 2 (Th2) polarization of iNK T cells using the synthetic glycolipid OCH significantly reduces mortality from IAS. This reduction in mortality is associated with the systemic elevation of the anti-inflammatory cytokine interleukin (IL)-13 and reduction of several proinflammatory cytokines within the spleen, notably interleukin (IL)-17. Finally, we show that treatment of sepsis with OCH in mice is accompanied by significantly reduced apoptosis of splenic T and B lymphocytes and macrophages, but not natural killer cells. We propose that modulation of iNK T cell responses towards a Th2 phenotype may be an effective therapeutic strategy in early sepsis. PMID:24965554

  17. Molecular structure and QSAR study on antispasmodic activity of some xanthoxyline derivatives.

    PubMed

    dos Santos, Rodrigo; Kuhnen, Carlos Alberto; Yunes, Rosendo Augusto

    2006-05-01

    Semi-empirical molecular orbital calculations at AM1 level were done with the aim to investigate the structure-activity relationships of antispasmodic activities of ten 2-(X-benzyloxy)-4,6-dimethoxyacetophenones with X = H, 4'-F, 4'-NO2, 4'-CH3, 4'-Cl, 3',4'-(CH3)2, 4'-OCH3, 4'-Br, 4'-OCH2C6H5, and 4'-C(CH3)3, against acetylcholine-induced contraction of the guinea pig ileum. The most significant quantum chemical descriptors for this series of compounds were the net atomic charges, nucleophilic and electrophilic frontier electron density, HOMO and LUMO orbitals, and reactivity indices. While no significant correlations were found employing molecular parameters such as heat of formation, dipole moment, molecular polarizability, and so on, good correlations were obtained using the reactivity indices of HOMO and LUMO orbitals at specific atoms of the molecules. These results indicate that the spatial distribution of HOMO and LUMO orbitals over these specific atoms play an important role for an increase of biological activity.

  18. Improving the thermostability of a methyl parathion hydrolase by adding the ionic bond on protein surface.

    PubMed

    Su, Yidan; Tian, Jian; Wang, Ping; Chu, Xiaoyu; Liu, Guoan; Wu, Ningfeng; Fan, Yunliu

    2011-10-01

    The thermostability of the methyl parathion hydrolase (MPH_OCH) from Ochrobactrum sp. M231 was improved using site-directed mutagenesis. Two prolines (Pro76 and Pro78) located on the protein surface were selected for mutations after inspection of the sequence alignment of MPH_OCH and OPHC2, a thermostable organophosphorus hydrolase from Pseudomonas pseudoalcaligenes C2-1. The temperature of the double-point mutant (P76D/P78K) at which the mutant lost 50% of its activity (T50) was approximately 68 °C, which is higher than that of WT enzyme (64 °C), P76D (67 °C), and P78K (59 °C). Structural analysis of P76D/P78K indicated that the substituted residues (Asp76 and Lys78) could generate an ionic bond and increase the structural electrostatic energy, which could then increase the stability of the protein. These results also suggest that the thermal stability of proteins could be improved by adding the ionic bond on protein surface.

  19. Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films

    PubMed Central

    Ciabocco, Michela; Berrettoni, Mario; Zamponi, Silvia

    2015-01-01

    Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH3)3SiOCH3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm-3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH3)3SiOCH3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN)64- at scan rates above 5 mVs-1 yielded currents controlled primarily by linear diffusion. Below 5 mVs-1, convection rather than the expected factor, radial diffusion, apparently limited the current. PMID:26167128

  20. Hydrogen production by coupled catalytic partial oxidation and steam methane reforming at elevated pressure and temperature

    NASA Astrophysics Data System (ADS)

    Chen, Luwei; Hong, Qi; Lin, Jianyi; Dautzenberg, F. M.

    Hydrogen production by coupled catalytic partial oxidation (CPO) and steam methane reforming of methane (OSMR) at industrial conditions (high temperatures and pressures) have been studied over supported 1 wt.% NiB catalysts. Mixture of air/CH 4/H 2O was applied as the feed. The effects of O 2:CH 4 ratio, H 2O:CH 4 ratio and the gas hourly space velocity (GHSV) on oxy-steam reforming (OSRM) were also studied. Results indicate that CH 4 conversion increases significantly with increasing O 2:CH 4 or H 2O:CH 4 ratio. However, the hydrogen mole fraction goes through a maximum, depending on reaction conditions, e.g., pressure, temperature and the feed gases ratios. Carbon deposition on the catalysts has been greatly decreased after steam addition. The supported 1 wt.% NiB catalysts exhibit high stability with 85% methane conversion at 15 bar and 800 °C during 70 h time-on-stream reaction (CH 4:O 2:H 2O:N 2 = 1:0.5:1:1.887). The thermal efficiency was increased from 35.8% by CPO (without steam) to 55.6%. The presented data would be useful references for further design of enlarged scale hydrogen production system.

  1. Theoretical and experimental study of methane steam reforming reactions over nickel catalyst

    NASA Astrophysics Data System (ADS)

    Pistonesi, C.; Juan, A.; Irigoyen, B.; Amadeo, N.

    2007-02-01

    In this work we perform DFT theoretical calculations of methane and steam interactions on Ni(1 1 1) surface. The calculations allow us to improve our understanding of the competition between these reactants by catalytic sites in methane steam reforming (MSR) process. For this purpose we compare theoretical results with kinetic measurements of MSR on a Ni(II)-Al(III) catalyst prepared from lamellar double hydroxides as precursor. This comparison shows that, for low H 2O/CH 4 ratios methane and water intermediate species adsorb on different catalytic sites. While CHO species adsorbs on top of Ni atom, OH one occupies preferentially a tri-coordinate surface site. On the other hand, for high H 2O/CH 4 ratios a competency between these species by Ni sites would establish, diminishing methane conversion. In addition competition between methane and steam for Ni sites would lead to a decrease in CO production. Nevertheless, intermediate species adsorbed on different active sites would produce CO 2, whatever the steam/methane ratio. Thus, it would be optimum steam concentration in hydrocarbon feed and active sites distribution on catalyst surface, which could maximize H 2 production and minimize CO selectivity. The theoretical findings agree with kinetic measurements, which show that maximum methane conversion depends on steam partial pressure in the feed; whereas always, selectivity to CO 2 increases and to CO diminishes.

  2. Nucleophilic substitution at silicon (SN2@Si) via a central reaction barrier.

    PubMed

    Bento, A Patrícia; Bickelhaupt, F Matthias

    2007-03-16

    It is textbook knowledge that nucleophilic substitution at carbon (SN2@C) proceeds via a central reaction barrier which disappears in the corresponding nucleophilic substitution reaction at silicon (SN2@Si). Here, we address the question why the central barrier disappears from SN2@C to SN2@Si despite the fact that these processes are isostructural and isoelectronic. To this end, we have explored and analyzed the potential energy surfaces (PES) of various Cl-+CR3Cl (R=H, CH3) and Cl-+SiR3Cl model reactions (R=H, CH3, C2H5, and OCH3). Our results show that the nature of the SN2 reaction barrier is in essence steric, but that it can be modulated by electronic factors. Thus, simply by increasing the steric demand of the substituents R around the silicon atom, the SN2@Si mechanism changes from its regular single-well PES (with a stable intermediate transition complex, TC), via a triple-well PES (with a pre- and a post-TS before and after the central TC), to a double-well PES (with a TS; R=OCH3), which is normally encountered for SN2@C reactions.

  3. Direct ab initio molecular dynamics study on a microsolvated SN2 reaction of OH-(H2O) with CH3Cl.

    PubMed

    Tachikawa, Hiroto

    2006-10-07

    Reaction dynamics for a microsolvated SN2 reaction OH-(H2O)+CH3Cl have been investigated by means of the direct ab initio molecular dynamics method. The relative center-of-mass collision energies were chosen as 10, 15, and 25 kcal/mol. Three reaction channels were found as products. These are (1) a channel leading to complete dissociation (the products are CH3OH+Cl- +H2O: denoted by channel I), (2) a solvation channel (the products are Cl-(H2O)+CH3OH: channel II), and (3) a complex formation channel (the products are CH3OH...H2O+Cl-: channel III). The branching ratios for the three channels were drastically changed as a function of center-of-mass collision energy. The ratio of complete dissociation channel (channel I) increased with increasing collision energy, whereas that of channel III decreased. The solvation channel (channel II) was minor at all collision energies. The selectivity of the reaction channels and the mechanism are discussed on the basis of the theoretical results.

  4. Direct ab initio molecular dynamics study on a microsolvated SN2 reaction of OH-(H2O) with CH3Cl

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto

    2006-10-01

    Reaction dynamics for a microsolvated SN2 reaction OH-(H2O)+CH3Cl have been investigated by means of the direct ab initio molecular dynamics method. The relative center-of-mass collision energies were chosen as 10, 15, and 25kcal/mol. Three reaction channels were found as products. These are (1) a channel leading to complete dissociation (the products are CH3OH+Cl-+H2O: denoted by channel I), (2) a solvation channel (the products are Cl-(H2O)+CH3OH: channel II), and (3) a complex formation channel (the products are CH3OH ⋯H2O+Cl-: channel III). The branching ratios for the three channels were drastically changed as a function of center-of-mass collision energy. The ratio of complete dissociation channel (channel I) increased with increasing collision energy, whereas that of channel III decreased. The solvation channel (channel II) was minor at all collision energies. The selectivity of the reaction channels and the mechanism are discussed on the basis of the theoretical results.

  5. Three-component one-pot synthesis of novel pyrido[2,3-d]pyrimidine indole substituted derivatives and DFT analysis

    NASA Astrophysics Data System (ADS)

    Rangel, Jovanni; Díaz-Uribe, Carlos; Rodriguez-Serrano, Angela; Zarate, Ximena; Serge, York; Vallejo, William; Nogueras, Manuel; Trilleras, Jorge; Quiroga, Jairo; Tatchen, Jörg; Cobo, Justo

    2017-06-01

    Pyridopyrimidines are heterocyclic aromatic compounds known by their antibacterial and medicinal properties. In this work, a series of pyrido[2,3-d]pyrimidine indole derivatives were synthesized by three-component one pot cyclocondensation Michael reaction between 2,6-diaminopirimidin-4(3H)-one, 3-(2-cyanoacetyl)indole and aromatic aldehydes in boiling acetic acid as solvent. The compounds differ with respect to the substituents of the aromatic aldehyde which are comprised by -C6H5, -4-ClC6H4, -4-NO2C6H4, -3,4-OCH2OC6H3, -3-OCH3,4-OH,5-NO2C6H2, and -3,4,5-tri-H3COC6H2, respectively. The compounds were synthesized with reasonable yields. They were characterized by and IR, mass, and NMR spectrometry. The protocol employed offers the convenient advantages of a one-step synthesis, considerable savings of solvents, and easy isolation of reaction products. In addition, DFT and TD-DFT quantum chemical calculations were used to characterize the geometry and electronic structure of the compounds.

  6. Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester.

    PubMed

    Duong, Nhung N; Wang, Bin; Sooknoi, Tawan; Crossley, Steven P; Resasco, Daniel E

    2017-07-10

    Acylation is an effective C-C bond-forming reaction to condense acetic acid and lignin-derived aromatic compounds into acetophenones, valuable precursors to fuels and chemicals. However, acetic acid is intrinsically an ineffective acylating agent. Here, we report that its acylation activity can be greatly enhanced by forming intermediate aromatic esters directly derived from acetic acid and phenolic compounds. Additionally, the acylation reaction was studied in the liquid phase over acid zeolites and was found to happen in two steps: 1) formation of an acylium ion and 2) C-C bond formation between the acylium ion and the aromatic substrate. Each of these steps may be rate-limiting, depending on the type of acylating agent and the aromatic substrate. Oxygen-containing substituents, such as -OH and -OCH3 , can activate aromatic substrates for step 2, with -OH> -OCH3 , whereas alkyl substituent -R cannot. At the same time, aromatic esters can rearrange to acetophenones by both an intramolecular pathway and, preferentially, an intermolecular one. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Interactions of nucleosides with CrO(4) (2-) and Cr(3+) as studied by electrospray ionization mass spectrometry.

    PubMed

    Frańska, Magdalena; Gierczyk, Karolina

    2008-06-01

    The interactions of CrO(4) (2-) and Cr(3+) with nucleosides studied by electrospray ionization mass spectrometry (ESI-MS) are reported. In water, the nucleosides which do not contain the NH(2) group form the unstable [M+HCrO(4)](-) anion. In the presence of a reducing agent, namely methanol, chromate anion forms stable complexes with nucleosides, [M+CH(3)CrO(4)](-) anions. The fragmentation of [M+CH(3)CrO(4)](-) anions involve elimination of the methanol molecule. Chromium cation-nucleoside complexes were not observed in water. In methanol solutions, adenosine and cytidine form [(M-H)+CrOCH(3)](+) and [(M-H)(2)+Cr](+) ions. Most probably, deprotonated imine tautomers form complexes in which a metal cation is simultaneously coordinated by two nitrogen atoms. Complexes containing chloride anions and a few methanol molecules were observed for other nucleosides. Guanosine and inosine form doubly charged ions of the type [M(2)+CrOCH(3)](2+) that probably contain a bond between the oxygen atom and the chromium cation, (HN(1)--C(6)==O)(2) (....)Cr(3+)).

  8. Synthesis, structural characterization, DFT studies and catalytic properties of dinuclear oxidovanadium(V) complexes derived from adipohydrazone ligands

    NASA Astrophysics Data System (ADS)

    Noei-Hootkani, Hashem; Karrari, Solmaz; Hosseini-Monfared, Hassan; Mayer, Peter; Notash, Behrouz

    2017-09-01

    Two new dinuclear oxidovanadium(V) complexes, [V2O2(L1)(OCH3)2(CH3OH)2]·2(CH3OH) (1) and [V2O2(L2)(OCH3)2(CH3OH)2]·2(CH3OH) (2), were synthesized from the reaction of VO(acac)2 and hexa-dentate N2O4-donor hydrazone ligands (H4L1 and H4L2) in methanol solvent. The ligands and complexes were characterized by elemental analysis and spectroscopic methods. Single crystal X-ray analysis of the brown crystals of complexes 1 and 2 indicated that these complexes are dinuclear oxidovanadium(V) complexes which the metal ions have distorted octahedral geometry. There are several strong and directed hydrogen bonding interactions in the crystal packing of 1 and 2 which stabilize their crystalline format. The catalytic activity of these complexes was tested in the oxidation of thioanisole using H2O2. These studies indicated both complexes have high catalytic activity in the oxidation of thioanisole. The complexes were further studied by DFT and TDDFT theoretical calculations.

  9. On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion

    SciTech Connect

    Francisco, J.

    1999-07-01

    There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.

  10. Atmospheric and combustion chemistry of dimethyl ether

    SciTech Connect

    Nielsen, O.J.; Egsgaard, H.; Larsen, E.; Sehested, J.; Wallington, T.J.

    1997-12-31

    It has been demonstrated that dimethyl ether (DME) is an ideal diesel fuel alternative. DME, CH{sub 3}OCH{sub 3}, combines good fuel properties with low exhaust emissions and low combustion noise. Large scale production of this fuel can take place using a single step catalytic process converting CH{sub 4} to DME. The fate of DME in the atmosphere has previously been studied. The atmospheric degradation is initiated by the reaction with hydroxyl radicals, which is also a common feature of combustion processes. Spectrokinetic investigations and product analysis were used to demonstrate that the intermediate oxy radical, CH{sub 3}OCH{sub 2}O, exhibits a novel reaction pathway of hydrogen atom ejection. The application of tandem mass spectrometry to chemi-ions based on supersonic molecular beam sampling has recently been demonstrated. The highly reactive ionic intermediates are sampled directly from the flame and identified by collision activation mass spectrometry and ion-molecule reactions. The mass spectrum reflects the distribution of the intermediates in the flame. The atmospheric degradation of DME as well as the unique fuel properties of a oxygen containing compound will be discussed.

  11. DFT Study on the Radical Anions Formed by Primaquine and Its Derivatives

    PubMed Central

    Liu, Haining; Walker, Larry A.

    2011-01-01

    The electron affinities (EA) of the 8-aminoquinoline antimalarial drug primaquine and several of its metabolites were studied using the density functional theory method. We first considered six substituents at the 5-position, −CH3, −OH, −OCH3, −Ph, −OPh and −CHO. We found that in the gas phase the adiabatic EAs are similar to that of the parent primaquine for the −CH3, −OH and −OCH3 substituents. In contrast, the −Ph, −OPh and −CHO substituents all markedly increase the adiabatic EA. However, only the −CHO substituted compound is predicted to form a stable covalently bound radical anion in the gas phase due to its significant positive vertical EA relative to that of the parent primaquine. In addition, when the 8-position is substituted by the N-hydroxyl group or a quinone-imine structure is formed, the electron capture ability is significantly increased. In aqueous solution, all these molecules have significantly larger adiabatic EAs than in the gas phase. In addition, all the vertical EAs are positive in aqueous solution. The implications of these findings for contributing to our mechanistic understanding of the red cell toxicity of 8-aminoquinoline compounds are further discussed. PMID:21699254

  12. Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants.

    PubMed

    Messina, Marco S; Axtell, Jonathan C; Wang, Yiqun; Chong, Paul; Wixtrom, Alex I; Kirlikovali, Kent O; Upton, Brianna M; Hunter, Bryan M; Shafaat, Oliver S; Khan, Saeed I; Winkler, Jay R; Gray, Harry B; Alexandrova, Anastassia N; Maynard, Heather D; Spokoyny, Alexander M

    2016-06-08

    We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B12(OCH2Ar)12 (Ar = Ph or C6F5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B12(OCH2C6F5)12 in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations.

  13. The New World whirligig beetles of the genus Dineutus Macleay, 1825 (Coleoptera, Gyrinidae, Gyrininae, Dineutini)

    PubMed Central

    Gustafson, Grey T.; Miller, Kelly B.

    2015-01-01

    Abstract All New World members of the whirligig beetle genus Dineutus Macleay, 1825 are treated. The New World Dineutus are found to be composed of 18 species and 6 subspecies: one species, Dineutus mexicanus Ochs, 1925, stat. n. is elevated from subspecies to species rank, and the subspecies Dineutus carolinus mutchleri Ochs, 1925, syn. n. is synonymized here with the typical form. Lectotypes are designated for Dineutus discolor Aubé, 1838, Dineutes metallicus Aubé, 1838, Dineutus solitarius Aubé, 1838, Dineutes analis Régimbart, 1883, and Gyrinus longimanus Olivier, 1795. Each taxonomic unit is provided with a taxonomic history, type locality, diagnosis, distribution, habitat information, and a discussion section. The aedeagus and male mesotarsal claws are illustrated, and dorsal and ventral habitus images of both sexes, for each species and subspecies are provided. General distribution maps are provided for all taxonimc units. A key to the genera of New World Gyrinidae, as well as all the New World Dineutus species is provided. General Dineutus anatomy as well as a clarification of homology and anatomical terms is included. PMID:25685002

  14. New uses for old complexes: The very first report on the trypanocidal activity of symmetric trinuclear ruthenium complexes.

    PubMed

    Possato, Bruna; Carneiro, Zumira Aparecida; de Albuquerque, Sérgio; Nikolaou, Sofia

    2017-11-01

    This work reports on the trypanocidal activity of a series of symmetric triruthenium complexes combined with azanaphthalene ligands of general formula [Ru3O(CH3COO)6(L)3]PF6 (L=(1) quinazoline (qui), (2) 5-nitroisoquinoline (5-nitroiq), (3) 5-bromoisoquinoline (5-briq), (4) isoquinoline (iq), (5) 5-aminoisoquinoline (5-amiq), and (6) 5,6,7,8-tetrahydroisoquinoline (thiq)). All complexes within the series presented in vitro trypanocidal activity against both the trypomastigote and amastigote forms of T. cruzi. The IC50 values obtained for complexes 1-6 ranged from 1.39 to 165.9μM for the trypomastigote form and from 1.06 to 53.16μM for the amastigote form. These values were lower than the values observed for the metallic core [Ru3O(CH3COO)6(CH3OH)3](+) itself and for the free ligands in all cases. Remarkably, complex 6 displayed lower IC50 values than the reference drug (benznidazole) for the acute (trypomastigote form) and chronic (amastigote form) phases of Chagas disease. These findings, combined with the low toxicity against healthy cells (LLK-MK2 strain) and a high SI value (Selectivity Index >10) make complex 6 an excellent candidate for in vivo tests. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Conformational Study of Dibenzyl Ether

    NASA Astrophysics Data System (ADS)

    Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hewett, Daniel M.; Zwier, Timothy S.

    2017-06-01

    Understanding the initial stages of polycyclic aromatic hydrocarbon (PAH) aggregation, the onset of soot formation, is an important goal on the pathway to cleaner combustion processes. PAHs with short alkyl chains, present in fuel-rich combustion environments, can undergo reactions that will chemically link aromatic rings together. One such example of a linked diaryl compound is dibenzyl ether, C_{6}H_{5}-CH_{2}-O-CH_{2}-C_{6}H_{5}. The -CH_{2}-O-CH_{2}- linkage has a length and flexibility well-suited to forming a π-stacked conformation between the two phenyl rings. In this talk, we will explore the single-conformation spectroscopy of dibenzyl ether under jet-cooled conditions in the gas phase. Laser-induced fluorescence, chirped pulse Fourier transform microwave (8-18 GHz region), and single-conformation infrared spectroscopy in the alkyl CH stretch region were all carried out on the molecule, thereby interrogating its full array of electronic, vibrational and rotational degrees of freedom. This work is the first step in a broader study to determine the extent of π-stacking in linked aryl compounds as a function of linkage and PAH size.

  16. Mechanism and kinetic properties of OH-initiated atmospheric oxidation degradation of methamidophos in the presence of O2/NO

    NASA Astrophysics Data System (ADS)

    Shi, Xiangli; Zhang, Ruiming; Zhang, Qingzhu; Wang, Wenxing

    2016-05-01

    Methamidophos is a member of the organophosphorus insecticides. In the present work, the mechanism of the OH radical-initiated atmospheric oxidation degradation of methamidophos and the possible degradation products were investigated with the aid of quantum chemical calculations. The geometrical parameters and vibrational frequencies were calculated at the MPWB1K/6-31+G(d,p) level. The energies of all the stationary points were carried out at the MPWB1K/6-311+G(3df,2p) level of theory. The rate constants of key elementary steps involved in the OH radical-initiated atmospheric degradation of methamidophos were calculated by meaning of the canonical variation transition-state (CVT) theory with the small curvature tunneling (SCT) correction over the possible atmospheric temperature range of 273-333 K. The rate-temperature formulas were fitted for the first time. The pre-exponential factor and the activation energy were obtained. Studies show that the OH additions from the trans-positions of the NH2 and OCH3 groups, the H abstractions from the SCH3 and OCH3 groups as well as the substitution reaction resulting in the products of CH3OP(O)OHNH2 and SCH3 are thermodynamically favorable reaction pathways for the reaction of methamidophos with OH radicals due to the low barrier and strong exothermicity.

  17. Fluorinated microemulsions: A study of the phase behavior and structure

    SciTech Connect

    LoNostro, P.; Choi, S.M.; Chen, S.H.; Ku, C.Y.

    1999-06-24

    Fluorinated surfactants have been studied for their peculiar property to form micellar aggregates in water and oils (hydrocarbons or fluorocarbons) and to produce stable microemulsions. Because of their capacity to dissolve large amounts of gases (such as oxygen and carbon dioxide) and for their characteristic physicochemical properties, fluorocarbons have been tested for specific medical purposes, and their microemulsions are among the most promising candidates for the production of suitable blood substitutes and other biocompatible fluids. The authors have synthesized a new partially fluorinated nonionic surfactant, namely, F(CF{sub 2}){sub 7}-CO-(OCH{sub 2}CH{sub 2}){sub 7.2}OCH{sub 3} (I), that forms stable microemulsions with water and perfluorocarbons such as perfluorooctane (PFO). In this paper the authors describe for the first time the phase behaviors of perfluorooctanoic acid (PFOA) in water/PFH and in water/PFO, and that of ester I in water/PFO. Small-angle neutron-scattering (SANS) experiments provide a detailed description of the microstructure of the H{sub 2}O/PFO/PFOA ternary system.

  18. One-pot solvothermal synthesis of a well-ordered layered sodium aluminoalcoholate complex: a useful precursor for the preparation of porous Al2O3 particles

    SciTech Connect

    Li, XS; Michaelis, VK; Ong, TC; Smith, SJ; McKay, I; Muller, P; Griffin, RG; Wang, EN

    2014-01-01

    One-pot solvothermal synthesis of a robust tetranuclear sodium hexakis(glycolato)tris(methanolato)aluminate complex Na-3[Al-4(OCH3)(3)(OCH2CH2O)(6)] via a modified yet rigorous base-catalyzed transesterification mechanism is presented here. Single crystal X-ray diffraction (SCXRD) studies indicate that this unique Al complex contains three pentacoordinate Al3+ ions, each bound to two bidentate ethylene glycolate chelators and one monodentate methanolate ligand. The remaining fourth Al3+ ion is octahedrally coordinated to one oxygen atom from each of the six surrounding glycolate chelators, effectively stitching the three pentacoordinate Al moieties together into a novel tetranuclear Al complex. This aluminate complex is periodically self-assembled into well-ordered layers normal to the [110] axis with the intra-/inter-layer bonding involving extensive ionic bonds from the three charge-counterbalancing Na+ cations rather than the more typical hydrogen bonding interactions as a result of fewer free hydroxyl groups present in its structure. It can also serve as a valuable precursor toward the facile synthesis of high-surface-area alumina powders using a very efficient rapid pyrolysis technique.

  19. Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

    PubMed Central

    Mehdi, B. Layla; Rutkowska, Iwona A.; Kulesza, Pawel J.

    2013-01-01

    Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)63− and Ru(NH3)63+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes. PMID:23935394

  20. OH Production from Reactions of Organic Peroxy Radicals with HO2 : Recent Studies on Ether-Derived Peroxy Radicals

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.; Kegley Owen, C. S.; Reynoldson, N.

    2013-12-01

    There is now ample evidence supporting significant formation of OH radicals in the reaction of HO2 with certain organic peroxy radicals (RO2). These reaction channels serve to promote radical propagation, and thus have the potential to alter HOx budgets and partitioning and hence tropospheric oxidative capacity. While much focus has been placed on OH production from reactions involving carbonyl-containing RO2 species, it is also the case that other oxygen- substituted peroxy species (e.g., CH3OCH2OO, HOCH2OO) likely generate OH in their reactions with HO2 (see ref. 1 and refs therein). In this work, the Cl-atom-initiated oxidation of two ethers, diethyl and diisopropyl ether, is investigated over ranges of conditions in an environmental chamber, using both FTIR and GC-FID methods for product quantification. Preliminary analysis suggests that significant OH production is occurring in the reaction of HO2 with CH3CH2OCH(OO)CH3, and also provides evidence for a rapid unimolecular reaction of diisopropyl ether-derived peroxy radicals. Details of these and other results will be described. 1. Orlando, J. J., and G. S. Tyndall, 2012: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chemical Society Reviews, 41, 6294-6317, doi: 10.1039/C2CS35166H.

  1. Ab Initio Investigation of Polyethylene Glycol Coating of TiO2 Surfaces

    PubMed Central

    2016-01-01

    In biomedical applications, TiO2 nanoparticles are generally coated with polymers to prevent agglomeration, improve biocompatibility, and reduce cytotoxicity. Although the synthesis processes of such composite compounds are well established, there is still a substantial lack of information on the nature of the interaction between the titania surface and the organic macromolecules. In this work, the adsorption of polyethylene glycol (PEG) on the TiO2 (101) anatase surface is modeled by means of dispersion-corrected density functional theory (DFT-D2) calculations. The two extreme limits of an infinite PEG polymer [−(OCH2CH2)n], on one side, and of a short PEG dimer molecule [H(OCH2CH2)2OH], on the other, are analyzed. Many different molecular configurations and modes of adsorption are compared at increasing surface coverage densities. At low and medium coverage, PEG prefers to lay down on the surface, while at full coverage, the adsorption is maximized when PEG molecules bind perpendicularly to the surface and interact with each other through lateral dispersions, following a mushroom to brush transition. Finally, we also consider the adsorption of competing water molecules at different coverage densities, assessing whether PEG would remain bonded to the surface or desorb in the presence of the aqueous solvent. PMID:28058086

  2. The Ontario Child Health Study: social adjustment and mental health of siblings of children with chronic health problems.

    PubMed

    Cadman, D; Boyle, M; Offord, D R

    1988-06-01

    There has been controversy concerning the type and amount of psychosocial maladjustment among the siblings of children with chronic physical health problems and disabilities. Most previous studies have been conducted in clinical populations, often from tertiary care centers. This paper reports the risks of psychiatric disorders and social adjustment problems of the siblings of chronically ill children found in the Ontario Child Health Study (OCHS). The OCHS was a general population survey of 3,294 children, 4-16 years of age, living in 1,869 randomly selected families in the Province of Ontario, Canada. A 2-fold risk in emotional disorders, including depression, anxiety, and obsessive-compulsive disorder, and a 1.6-fold increase in risk in poor peer relationships were found. However, risks for conduct disorder, somatization disorder (measured only in 12- to 16-year olds), attention deficit disorder-hyperactivity, and one or more psychiatric disorders were not elevated. Moreover, no increased risks of adjustment problems, including social isolation, low participation in leisure activities, low competence in usual childhood recreational activities or school problems, were observed. Clinicians treating chronically ill children should assess the mental health and adjustment of their siblings without an expectation bias that problems will be found.

  3. Sensitization of NIR luminescence of Yb(3+) by Zn(2+) chromophores in heterometallic complexes with a bridging Schiff-base ligand.

    PubMed

    Pushkarev, Anatoly P; Balashova, Tatyana V; Kukinov, Andrey A; Arsenyev, Maxim V; Yablonskiy, Artem N; Kryzhkov, Denis I; Andreev, Boris A; Rumyantcev, Roman V; Fukin, Georgy K; Bochkarev, Mikhail N

    2017-08-08

    Herein, complexes [ZnL]2 (1), {(H2O)Zn(μ-L)Yb[OCH(CF3)2]3} (2), {[(CF3)2HCO]Zn(μ-L)Yb[OCH(CF3)2](μ-OH)}2 (3), and [(H2O)Ln2(L)3] (Ln = Yb (4) and Gd (5)) containing a bridging Schiff-base ligand (H2L = N,N'-bis(3-methoxy salicylidene)phenylene-1,2-diamine) were synthesized. The compounds 1-4 were structurally characterized. The ytterbium derivatives 2-4 exhibited bright NIR metal-centred photoluminescence (PL) of Yb(3+) ion under one- (λex = 380 nm) and two-photon (λex = 750 nm) excitation. The superior luminescence properties of complex 2, which was suggested as a marker for NIR bioimaging, were explained via the strong absorption of the 375 nm LMCT state of the ZnL chromophore, efficient energy transfer from ZnL towards Yb(3+) through a reversible ligand-to-lanthanide electron transfer process, and absence of luminescence quenchers (C-H and O-H groups) in the first coordination sphere of the rare-earth atom.

  4. Theoretical study of the O···Cl interaction in fluorinated dimethyl ethers complexed with a Cl atom: is it through a two-center-three-electron bond?

    PubMed

    Zeegers-Huyskens, Therese; Lily, Makroni; Sutradhar, Dipankar; Chandra, Asit K

    2013-08-22

    Theoretical investigations are carried out on the interaction between fluorinated dimethyl ethers (FDME, nF = 0-4) and the Cl atom. Short intermolecular O···Cl distances between 2.401 and 2.938 Å reveal the formation of a new class of complexes. The interaction energies calculated with the G2(MP2) method range between -9.1 (nF = 4) and -26.0 (nF = 0) kJ/mol. The charge transfer occurring from the ethers to atomic Cl is moderate and ranges between 0.012 e (nF = 4) to 0.188 e (nF = 0). The binding energies are linearly related to the proton affinity, to the charge transfer (CT) occurring in the molecular system and inversely proportional to the ionization potential and electron affinity (IP-EA) values. The CT and spin density data indicate substantial two-center-three-electron O···Cl interaction in CH3OCH3···Cl and CH3OCH2F···Cl systems, whereas for highly fluorinated ethers the interaction is predominantly electrostatic in nature. The formation of the complex results in a contraction of the CH bonds, especially in the gauche position. The blue shifts of the C-H stretching vibrations calculated in the partially deuterated isotopomers range between 2 and 54 cm(-1) and are correlated to the variation of the CH distances.

  5. Model biogas steam reforming in a thin Pd-supported membrane reactor to generate clean hydrogen for fuel cells

    NASA Astrophysics Data System (ADS)

    Iulianelli, A.; Liguori, S.; Huang, Y.; Basile, A.

    2015-01-01

    Steam reforming of a model biogas mixture is studied for generating clean hydrogen by using an inorganic membrane reactor, in which a composite Pd/Al2O3 membrane separates part of the produced hydrogen through its selective permeation. The characteristics of H2 perm-selectivity of the fresh membrane is expressed in terms of H2/N2 ideal selectivity, in this case equal to 4300. Concerning biogas steam reforming reaction, at 380 °C, 2.0 bar H2O:CH4 = 3:1, GHSV = 9000 h-1 the permeate purity of the recovered hydrogen is around 96%, although the conversion (15%) and hydrogen recovery (>20%) are relatively low; on the contrary, at 450 °C, 3.5 bar H2O:CH4 = 4:1, GHSV = 11000 h-1 the conversion is increased up to more than 30% and the recovery of hydrogen to about 70%. This novel work constitutes a reference study for new developments on biogas steam reforming reaction in membrane reactors.

  6. Group II tris(glycolato)silicates as precursors to silicate glasses and ceramics

    SciTech Connect

    Kansal, P.; Laine, R.M.

    1995-03-01

    Group II tris(glycolato)silicates, MSi(OCH{sub 2}CH{sub 2}O){sub 3} (where M = Ba, Ca, Mg), can be synthesized directly by reaction of silica with ethylene glycol and alkaline-earth (group II) oxides at 200 C. These hexa-alkoxy silicates serve as precursors to silicate glass and ceramic powders. They are readily modified by exchange with longer-chain diols into proper precursors. These rheologically useful precursors may provide access to silicate or aluminosilicate powders, thin films, fibers, and coatings. Thus, the authors have examined the utility of hexacoordinate glycolatosilicates as model precursors. Pyrolysis of the compounds, MSi(OCH{sub 2}CH{sub 2})O{sub 3}, in air transforms them to their anticipated ceramic products, MO{center_dot}SiO{sub 2}. The phase transformation and chemical changes that occur during pyrolysis were characterized using X-ray powder diffractometry (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The hexacoordinate glycolatosilicates oxidatively decompose at {approx}300 C to form amorphous materials. Moderate to significant quantities of the group II carbonates, MCO{sub 3} (15--50 wt%), form coincidentally as the amorphous intermediates trap CO{sub 2} generated by ligand oxidation. At {approx}900 C, the amorphous materials crystallize into the expected, phase-pure, MO{center_dot}SiO{sub 2}.

  7. T helper type 2-polarized invariant natural killer T cells reduce disease severity in acute intra-abdominal sepsis.

    PubMed

    Anantha, R V; Mazzuca, D M; Xu, S X; Porcelli, S A; Fraser, D D; Martin, C M; Welch, I; Mele, T; Haeryfar, S M M; McCormick, J K

    2014-11-01

    Sepsis is characterized by a severe systemic inflammatory response to infection that is associated with high morbidity and mortality despite optimal care. Invariant natural killer T (iNK T) cells are potent regulatory lymphocytes that can produce pro- and/or anti-inflammatory cytokines, thus shaping the course and nature of immune responses; however, little is known about their role in sepsis. We demonstrate here that patients with sepsis/severe sepsis have significantly elevated proportions of iNK T cells in their peripheral blood (as a percentage of their circulating T cells) compared to non-septic patients. We therefore investigated the role of iNK T cells in a mouse model of intra-abdominal sepsis (IAS). Our data show that iNK T cells are pathogenic in IAS, and that T helper type 2 (Th2) polarization of iNK T cells using the synthetic glycolipid OCH significantly reduces mortality from IAS. This reduction in mortality is associated with the systemic elevation of the anti-inflammatory cytokine interleukin (IL)-13 and reduction of several proinflammatory cytokines within the spleen, notably interleukin (IL)-17. Finally, we show that treatment of sepsis with OCH in mice is accompanied by significantly reduced apoptosis of splenic T and B lymphocytes and macrophages, but not natural killer cells. We propose that modulation of iNK T cell responses towards a Th2 phenotype may be an effective therapeutic strategy in early sepsis.

  8. Competing Noncovalent Host-guest Interactions and H/D Exchange: Reactions of Benzyloxycarbonyl-Proline Glycine Dipeptide Variants with ND3

    NASA Astrophysics Data System (ADS)

    Miladi, Mahsan; Olaitan, Abayomi D.; Zekavat, Behrooz; Solouki, Touradj

    2015-11-01

    A combination of density functional theory calculations, hydrogen/deuterium exchange (HDX) reactions, ion mobility-mass spectrometry, and isotope labeling tandem mass spectrometry was used to study gas-phase "host-guest" type interactions of a benzyloxycarbonyl (Z)-capped proline (P) glycine (G) model dipeptide (i.e., Z-PG) and its various structural analogues with ND3. It is shown that in a solvent-free environment, structural differences between protonated and alkali metal ion (Na+, K+, or Cs+)-complexed species of Z-PG affect ND3 adduct formation. Specifically, [Z-PG + H]+ and [Z-PG-OCH3 + H]+ formed gas-phase ND3 adducts ([Z-PG (or Z-PG-OCH3) + H + ND3]+) but no ND3 adducts were observed for [Z-PG + alkali metal]+ or [Z-PG + H - CO2]+. Experimentally measured and theoretically calculated collision cross sections (CCSs) of protonated and alkali metal ion-complexed Z-PG species showed similar trends that agreed with the observed structural differences from molecular modeling results. Moreover, results from theoretical ND3 affinity calculations were consistent with experimental HDX observations, indicating a more stable ND3 adduct for [Z-PG + H]+ compared to [Z-PG + alkali metal]+ species. Molecular modeling and experimental MS results for [Z-PG + H]+ and [Z-PG + alkali metal]+ suggest that optimized cation-π and hydrogen bonding interactions of carbonyl groups in final products are important for ND3 adduct formation.

  9. Surface chemistry of boron-doped SiO{sub 2} CVD: Enhanced uptake of tetraethyl orthosilicate by hydroxyl groups bonded to boron

    SciTech Connect

    Bartram, M.E.; Moffat, H.K.

    1993-12-31

    Insight into how dopants can enhance deposition rates has been obtained by comparing reactivities of tetraethyl orthosilicate (TEOS, Si(OCH{sub 2}CH{sub 3}){sub 4}) with silanol and boranol groups on SiO{sub 2}. This comparison is relevant for boron-doped SiO{sub 2} film growth from TEOS and trimethyl borate (TMB, B(OCH{sub 3}){sub 3}) sources since boranols and silanols are expected to be present on surface during the (CVD). A silica substrate having coadsorbed deuterated silanols (SIOD) and boranols (BOD) was reacted with TEOS in a cold-wall reactor in the mTorr pressure regime at 1000K. Reactions were followed with Fourier transform infrared spectroscopy. Use of deuterated hydroxyls allowed consumption of hydroxyls by TEOS chemisorption to be distinguished from concurrent formation of SIOH and BOH that results from TEOS decomposition. It was found that TEOS reacts with BOD at twice the rate observed for SIOD demonstrating that hydroxyl groups bonded to boron increase the rate of TEOS chemisorption. Surface ethoxy groups produced by chemisorption of TEOS decompose at a slower rate in the presence of TMB decomposition products. Possible dependencies on reactor geometries and other deposition conditions may determine which of these two competing effects will control deposition rates. This may explain (in part) why the rate enhancement effect is not always observed in boron-doped SiO{sub 2} CVD processes.

  10. Uric and 1-methyluric acids: metabolic wastes or antiradical protectors?

    PubMed

    León-Carmona, Jorge Rafael; Galano, Annia

    2011-12-29

    The reactions of uric and 1-methyluric acids in nonpolar environments, as well as those of the corresponding urate anions in aqueous solution, with (•)OH, (•)OCH(3), (•)OOH, and (•)OOCH(3) have been studied using the density functional theory. Different mechanisms of reactions have been taken into account, and their relative importance on the antiradical activity of these compounds is analyzed. Both uric and methyluric acids are better scavengers in aqueous solution than in nonpolar media, which indicates that the urate anions are the most active species. The free radical scavenging activity of the studied compounds was found to be excellent for (•)OH, and very good for (•)OCH(3). In addition, 1-methyluric acid is predicted to moderately protect against peroxyl oxidation, while the protective effects of uric acid against these particular species are not expected to be significant. In addition, 1-methyluric acid was found to be a better radical scavenger than its precursor, caffeine, suggesting that the antiradical activity of the latter might be explained by the action of its metabolites, rather than by its direct activity. © 2011 American Chemical Society

  11. The rate of charge tunneling is insensitive to polar terminal groups in self-assembled monolayers in Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn junctions.

    PubMed

    Yoon, Hyo Jae; Bowers, Carleen M; Baghbanzadeh, Mostafa; Whitesides, George M

    2014-01-08

    This paper describes a physical-organic study of the effect of uncharged, polar, functional groups on the rate of charge transport by tunneling across self-assembled monolayer (SAM)-based large-area junctions of the form Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn. Here Ag(TS) is a template-stripped silver substrate, -M- and -T are "middle" and "terminal" functional groups, and EGaIn is eutectic gallium-indium alloy. Twelve uncharged polar groups (-T = CN, CO2CH3, CF3, OCH3, N(CH3)2, CON(CH3)2, SCH3, SO2CH3, Br, P(O)(OEt)2, NHCOCH3, OSi(OCH3)3), having permanent dipole moments in the range 0.5 < μ < 4.5, were incorporated into the SAM. A comparison of the electrical characteristics of these junctions with those of junctions formed from n-alkanethiolates led to the conclusion that the rates of charge tunneling are insensitive to the replacement of terminal alkyl groups with the terminal polar groups in this set. The current densities measured in this work suggest that the tunneling decay parameter and injection current for SAMs terminated in nonpolar n-alkyl groups, and polar groups selected from common polar organic groups, are statistically indistinguishable.

  12. Ion-molecule reactions involving HCO+ and N2H+: Isotopologue equilibria from new theoretical calculations and consequences for interstellar isotope fractionation

    NASA Astrophysics Data System (ADS)

    Mladenović, M.; Roueff, E.

    2014-06-01

    Aims: We revisit with new augmented accuracy the theoretical dynamics of basic isotope exchange reactions involved in the 12C/13C, 16O/18O, and 14N/15N balance because these reactions have already been studied experimentally in great detail. Methods: Electronic structure methods were employed to explore potential energy surfaces, full-dimensional rovibrational calculations to compute rovibrational energy levels that are numerically exact, and chemical network models to estimate the abundance ratios under interstellar conditions. Results: New exothermicities, derived for HCO+ reacting with CO, provide rate coefficients markedly different from previous theoretical values in particular at low temperatures, resulting in new abundance ratios relevant for carbon chemistry networks. In concrete terms, we obtain a reduction in the abundance of H12C18O+ and an increase in the abundance of H13C16O+ and D13C16O+. In all studied cases, the reaction of the ion with a neutral polarizable molecule proceeds through the intermediate proton-bound complex found to be very stable. For the complexes OCH+··· CO, OCH+··· OC, COHOC+, N2··· HCO+, N2H+··· OC, and N2HN2+, we also calculated vibrational frequencies and dissociation energies. Conclusions: The linear proton-bound complexes possess sizeable dipole moments, which may facilitate their detection.

  13. One-pot Solvothermal Synthesis of Well-ordered Layered Sodium Aluminoalcoholate Complex: A Useful Precursor for the Preparation of Porous Al2O3 Particles.

    PubMed

    Li, Xiansen; Michaelis, Vladimir K; Ong, Ta-Chung; Smith, Stacey J; McKay, Ian; Müller, Peter; Griffin, Robert G; Wang, Evelyn N

    2014-04-14

    One-pot solvothermal synthesis of a robust tetranuclear sodium hexakis(glycolato)tris(methanolato)aluminate complex Na3[Al4(OCH3)3(OCH2CH2O)6] via a modified yet rigorous base-catalyzed transesterification mechanism is presented here. Single crystal X-ray diffraction (SCXRD) studies indicate that this unique Al complex contains three penta-coordinate Al(3+) ions, each bound to two bidentate ethylene glycolate chelators and one monodentate methanolate ligand. The remaining fourth Al(3+) ion is octahedrally coordinated to one oxygen atom from each of the six surrounding glycolate chelators, effectively stitching the three penta-coordinate Al moieties together into a novel tetranuclear Al complex. This aluminate complex is periodically self-assembled into well-ordered layers normal to the [110] axis with the intra-/inter-layer bindings involving extensive ionic bonds from the three charge-counterbalancing Na(+) cations rather than the more typical hydrogen bonding interactions as a result of the fewer free hydroxyl groups present in its structure. It can also serve as a valuable precursor toward the facile synthesis of high-surface-area alumina powders using a very efficient rapid pyrolysis technique.

  14. Mechanistic studies of CO2 reduction to methanol mediated by an N-heterocyclic germylene hydride.

    PubMed

    Tan, Gengwen; Wang, Wenyuan; Blom, Burgert; Driess, Matthias

    2014-04-28

    The labile germylene hydride L(Cy)GeH is capable of activating CO2 affording the corresponding formate L(Cy)GeOCH([double bond, length as m-dash]O) (2) (L(Cy) = cyclo-C6H8-1-NAr-2-C(Ph)NAr, Ar = 2,6-iPr2C6H3). Compound and the previously reported LGeOCH([double bond, length as m-dash]O) (L = CH(MeC[double bond, length as m-dash]NAr)2, Ar = 2,6-iPr2C6H3) (2) could be further converted to methanol with the AlH3 · NMe3 alane-amine adduct as a hydrogen source upon workup with water. A plausible mechanism for the conversion of the formate complexes to methanol is proposed based on additional results from the conversion of with the milder hydride delivery agent LAlH2.

  15. Modification of Different Zirconium Propoxide Precursors by Diethanolamine. Is There a Shelf Stability Issue for Sol-Gel Applications?

    PubMed Central

    Spijksma, Gerald I.; Blank, Dave H. A.; Bouwmeester, Henny J. M.; Kessler, Vadim G.

    2009-01-01

    Modification of different zirconium propoxide precursors with H2dea was investigated by characterization of the isolated modified species. Upon modification of zirconium n-propoxide and [Zr(OnPr)(OiPr)3(iPrOH)]2 with ½ a mol equivalent of H2dea the complexes [Zr2(OnPr)6(OCH2CH2)2NH]2 (1) and [Zr2(OnPr)2(OiPr)4(OCH2CH2)2NH]2 (2) were obtained. However, 1H-NMR studies of these tetranuclear compounds showed that these are not time-stable either in solution or solid form. The effect of this time instability on material properties is demonstrated by light scattering and TEM experiments. Modification of zirconium isopropoxide with either ½ or 1 equivalent mol of H2dea results in formation of the trinuclear complex, Zr{η3μ2-NH(C2H4O)2}3[Zr(OiPr)3]2(iPrOH)2 (3) countering a unique nona-coordinated central zirconium atom. This complex 3 is one of the first modified zirconium propoxide precursors shown to be stable in solution for long periods of time. The particle size and morphology of the products of sol-gel synthesis are strongly dependent on the time factor and eventual heat treatment of the precursor solution. Reproducible sol-gel synthesis requires the use of solution stable precursors. PMID:20087472

  16. Discrepancy Between Experimental and Theoretical Predictions of the Adiabaticity of Ti(+) +CH3 OH.

    PubMed

    Sweeny, Brendan C; Ard, Shaun G; McDonald, David C; Martinez, Oscar; Viggiano, Albert A; Shuman, Nicholas S

    2017-09-04

    The reaction between Ti(+) and methanol (CH3 OH) is a model system for competition between activation of C-O, C-H, and O-H bonds and of the role of excited electronic pathways in catalytic processes. Herein, we use experimental kinetics, quantum chemical calculations, and statistical modeling to identify the critical features of the reaction's potential energy surface. Experimental kinetics data between 300 and 600 K shows the reaction largely proceeds through C-O bond activation, yielding TiOH(+) and TiO(+) . Products of the O-H activation pathway, TiOCH2(+) and TiOCH3(+) are minor, whereas C-H bond activation is not observed at thermal energies. Statistical modeling well-reproduces the experimental results and offers insight into the reaction mechanism. Notably, efficient spin-crossing along the C-O activation pathway is required to produce the observed product distribution, in contrast to a previous estimate of inefficient crossing based on calculation of a small spin-orbit coupling constant. This discrepancy highlights a potential limitation of simple models within the Landau-Zener framework, which are commonly used to calculate surface-crossing probabilities in reactive systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Mechanistic study of atomic layer deposition of Al{sub x}Si{sub y}O thin film via in-situ FTIR spectroscopy

    SciTech Connect

    Cho, Jea; Kim, Taeseung; Seegmiller, Trevor; Chang, Jane P.

    2015-09-15

    A study of surface reaction mechanism on atomic layer deposition (ALD) of aluminum silicate (Al{sub x}Si{sub y}O) was conducted with trimethylaluminum (TMA) and tetraethoxysilane (TEOS) as precursors and H{sub 2}O as the oxidant. In-situ Fourier transform infrared spectroscopy (FTIR) was utilized to elucidate the underlying surface mechanism that enables the deposition of Al{sub x}Si{sub y}O by ALD. In-situ FTIR study revealed that ineffective hydroxylation of the surface ethoxy (–OCH{sub 2}CH{sub 3}) groups prohibits ALD of SiO{sub 2} by TEOS/H{sub 2}O. In contrast, effective desorption of the surface ethoxy group was observed in TEOS/H{sub 2}O/TMA/H{sub 2}O chemistry. The presence of Al-OH* group in vicinity of partially hydroxylated ethoxy (–OCH{sub 2}CH{sub 3}) group was found to propagate disproportionation reaction, which results in ALD of Al{sub x}Si{sub y}O. The maximum thickness from incorporation of SiO{sub x} from alternating exposures of TEOS/H{sub 2}O chemistry in Al{sub x}Si{sub y}O was found to be ∼2 Å, confirmed by high resolution transmission electron microscopy measurements.

  18. The New World whirligig beetles of the genus Dineutus Macleay, 1825 (Coleoptera, Gyrinidae, Gyrininae, Dineutini).

    PubMed

    Gustafson, Grey T; Miller, Kelly B

    2015-01-01

    All New World members of the whirligig beetle genus Dineutus Macleay, 1825 are treated. The New World Dineutus are found to be composed of 18 species and 6 subspecies: one species, Dineutusmexicanus Ochs, 1925, stat. n. is elevated from subspecies to species rank, and the subspecies Dineutuscarolinusmutchleri Ochs, 1925, syn. n. is synonymized here with the typical form. Lectotypes are designated for Dineutusdiscolor Aubé, 1838, Dineutesmetallicus Aubé, 1838, Dineutussolitarius Aubé, 1838, Dineutesanalis Régimbart, 1883, and Gyrinuslongimanus Olivier, 1795. Each taxonomic unit is provided with a taxonomic history, type locality, diagnosis, distribution, habitat information, and a discussion section. The aedeagus and male mesotarsal claws are illustrated, and dorsal and ventral habitus images of both sexes, for each species and subspecies are provided. General distribution maps are provided for all taxonimc units. A key to the genera of New World Gyrinidae, as well as all the New World Dineutus species is provided. General Dineutus anatomy as well as a clarification of homology and anatomical terms is included.

  19. Capsaicin, a tasty free radical scavenger: mechanism of action and kinetics.

    PubMed

    Galano, Annia; Martínez, Ana

    2012-01-26

    The free radical scavenging activity of capsaicin (CAP), which is the pungent component of hot chili peppers, has been studied in aqueous and lipid solutions, using the density functional theory. Different mechanisms of reaction have been considered: single electron transfer (SET), hydrogen transfer (HT), and radical adduct formation (RAF). Rate constants and branching ratios of the different channels of reaction are provided, as well as an interpretation of the UV-vis spectra. CAP is predicted to react faster in aqueous solution than in nonpolar media with oxygenated free radicals, and it was found to be a more efficient scavenger than melatonin and caffeine. It was also found that while SET does not contribute to the overall reactivity of CAP toward (•)OOH, (•)OOCH(3), and (•)OCH(3) radicals, it might be important for the reactions with more electrophilic radicals such as (•)OH, (•)OCCl(3), and (•)OOCCl(3). The main process, responsible for the peroxyl scavenging activity of CAP, was found to be the HT from the OH phenolic group. For the reaction with (•)OCH(3), on the other hand, the HT from allylic sites are predicted to be the main channels of reaction. In this particular case a wider product distribution is predicted. This supports the role of the reacting free radical on the preponderant mechanism of action of free radical scavengers.

  20. Synthesis and biological evaluation of pyrazolylthiazole carboxylic acids as potent anti-inflammatory-antimicrobial agents.

    PubMed

    Khloya, Poonam; Kumar, Satish; Kaushik, Pawan; Surain, Parveen; Kaushik, Dhirender; Sharma, Pawan K

    2015-03-15

    Current Letter presents design, synthesis and biological evaluation of a novel series of pyrazolylthiazole carboxylates 1a-1p and corresponding acid derivatives 2a-2p. All 32 novel compounds were tested for their in vivo anti-inflammatory activity by carrageenan-induced rat paw edema method as well as for in vitro antimicrobial activity. All the tested compounds exhibited excellent AI activity profile. Three compounds 1p (R=Cl, R(1)=Cl), 2c (R=H, R(1)=F) and 2n (R=Cl, R(1)=OCH3) were identified as potent anti-inflammatory agents exhibiting edema inhibition of 93.06-89.59% which is comparable to the reference drug indomethacin (91.32%) after 3h of carrageenan injection while most of the other compounds displayed inhibition ⩾80%. In addition, pyrazolylthiazole carboxylic acids (2a-2p) also showed good antimicrobial profile. Compound 2h (R=OCH3, R(1)=Cl) showed excellent antimicrobial activity (MIC 6.25μg/mL) against both Gram positive bacteria comparable with the reference drug ciprofloxacin (MIC 6.25μg/mL).

  1. Mechanistic and kinetic study on the reactions of coumaric acids with reactive oxygen species: a DFT approach.

    PubMed

    Garzón, Andrés; Bravo, Iván; Barbero, Antonio J; Albaladejo, José

    2014-10-08

    The mechanism and kinetics of reactions between coumaric acids and a series of reactive oxygen species ((•)OX) was studied through the density functional theory (DFT). H atom abstraction from -OH and -COOH groups and addition to the nonaromatic double bond were the most representative reaction pathways chosen for which free energy barriers and rate constants were calculated within the transition state theory (TST) framework. From these calculations, it was estimated that (•)OH > (•)OCH3 > (•)OOH > (•)OOCH3 is the order of reactivity of (•)OX with any coumaric acid. The highest rate constant was estimated for p-coumaric acid + (•)OH reaction, whereas the rest of the (•)OX species are more reactive with o-coumaric acid. On the basis of the calculated rate constants, H abstraction from a -OH group should be the main mechanism for the reactions involving (•)OCH3, (•)OOH, and (•)OOCH3 radicals. Nevertheless, the addition mechanism, which sometimes is not considered in theoretical studies on reactions of phenolic compounds with electrophilic species, could play a relevant role in the global mechanism of coumaric acid + (•)OH reactions.

  2. Lewis acid-base adducts of group 13 elements: synthesis, structure and reactivity toward benzaldehyde.

    PubMed

    Ganesamoorthy, C; Matthias, M; Bläser, D; Wölper, C; Schulz, S

    2016-07-28

    Lewis acid-base adducts [LGa-M(C6F5)3] (M = B 1, Al 2, Ga 3) were prepared by the reaction of gallanediyl LGa {L = HC[C(Me)N(2,6-i-Pr2C6H3)]2} with the Lewis acids M(C6F5)3 (M = B, Al, Ga). Benzaldehyde reacts with [LGa-M(C6F5)3] (M = B 1, Al 2) at room temperature with the insertion and formation of [LGa(C6F5){CH(Ph)(OB(C6F5)2)}] (4) and the zwitterionic species [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] (5), respectively, which was found to decompose at 80 °C with the formation of {(C6F5)2Al(OCH2Ph)}2 (6). Any attempts to isolate the insertion complex of [LGa-Ga(C6F5)3] with benzaldehyde failed and only {(C6F5)2Ga(OCH2Ph)}2 (7) was isolated at elevated temperatures. 2-5 and 7 were structurally characterized by heteronuclear NMR spectroscopy and single crystal X-ray diffraction.

  3. Preparation and electrochemical performance of polyphosphazene based salt-in-polymer electrolyte membranes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Jankowsky, S.; Hiller, M. M.; Wiemhöfer, H.-D.

    2014-05-01

    This work presents a detailed study of the electrochemical performance of polyphosphazene based electrolyte membranes consisting of a linear polymer with -(Ndbnd PR2)- units, grafted with ethylene oxide side chains of the type R = -(OCH2CH2)3OCH3 and containing LiTFSI and LiBOB as dissolved lithium salts. The average molecular weight was 105 g mol-1. Mechanical stability was achieved by UV induced in-situ cross-linking of the thin polymer electrolyte films. Favorable properties of this type of polymer electrolytes are the good thermal and electrochemical stability of the electrolyte membranes, the broad electrochemical stability window ranging between 0 V and 4.7 V versus the Li/Li+ reference and a very good interface stability at lithium metal electrodes where a stable SEI was formed during initial contact. Total ionic conductivities up to 10-4 S cm-1 were measured at 30 °C. The transference numbers of lithium ions at 50 °C ranged between 0.06 and 0.07 and hence are lower by a factor of about three as compared to other typical polymer electrolytes. Nevertheless, the partial lithium ion conductivity estimated from the product of total conductivity and lithium ion transference number is as high or slightly higher compared to PEO based polymer electrolytes.

  4. High-performance Ti/BDD electrodes for pollutant oxidation.

    PubMed

    Chen, Xueming; Chen, Guohua; Gao, Furong; Yue, Po Lock

    2003-11-01

    Deposition of stable boron-doped diamond (BDD) films on Ti substrates is believed to be very difficult. In the present study, the stability of Ti/BDD electrodes has been significantly improved by using an organic additive, CH2(OCH3)2. The improved electrodes had service lives of 175-264 h under accelerated life test conditions, which are 2.3-3.0 times longer than the service lives of electrodes prepared with the conventional H2 + CH4 mixture. Raman spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) examinations demonstrated thatthe films had well-defined diamond features. The current efficiency (CE) obtained on Ti/BDD was 46.9-78.5% in oxidizing acetic acid, maleic acid, phenol, and dyes, which is 1.6-4.3-fold higher than that obtained on the typical Ti/ Sb2O5-SnO2 electrode. We used a Ti/BDD electrode prepared with H2 + CH4 + CH2(OCH3)2 for over 300 h; its activity remained superior. The successful development of stable and active Ti/BDD electrodes significantly increases the feasibility of industrial applications of anodic oxidation in wastewater treatment.

  5. Magneto-Structural Analysis of Iron(III) Keggin Polyoxometalates.

    PubMed

    Bandeira, Nuno A G; Sadeghi, Omid; Woods, Toby J; Zhang, Yuan-Zhu; Schnack, Jürgen; Dunbar, Kim; Nyman, May; Bo, Carles

    2017-02-16

    A computational study and magnetic susceptibility measurements of three homonuclear Fe(III) Keggin structures are herein presented: the [FeO4@Fe12F24(μ-OCH3)12](5-) anion (1), the [Bi6{FeO4@Fe12O12(OH)12}(μ-O2CCCl3)12](+) cation (2) and its polymorph [Bi6{FeO4@Fe12O12(OH)10(H2O)2}(μ-O2CCF3)10](3+) (3). These results are contrasted with the exchange interactions present in the previously characterized [Fe6(OH)3Ge2W18O68(OH)6](11-) and [H12As4Fe8W30O120(H2O)2](4-) anions. The computational analysis shows that the most significant antiferromagnetic spin coupling takes place at the junction between each of the {Fe3O6(OH)3}/{Fe3F6(OCH3)3} framework motifs, a possibility that had been previously discarded in the literature on the basis of the Fe-Fe distances. For all the examined iron(III) Keggin structures, it is found that the magnitude of the magnetic couplings within each structural subunit follows the same trend.

  6. Abolishment of N-glycan mannosylphosphorylation in glyco-engineered Saccharomyces cerevisiae by double disruption of MNN4 and MNN14 genes.

    PubMed

    Kim, Yeong Hun; Kang, Ji-Yeon; Gil, Jin Young; Kim, Sang-Yoon; Shin, Keun Koo; Kang, Hyun Ah; Kim, Jeong-Yoon; Kwon, Ohsuk; Oh, Doo-Byoung

    2017-04-01

    Mannosylphosphorylated glycans are found only in fungi, including yeast, and the elimination of mannosylphosphates from glycans is a prerequisite for yeast glyco-engineering to produce human-compatible glycoproteins. In Saccharomyces cerevisiae, MNN4 and MNN6 genes are known to play roles in mannosylphosphorylation, but disruption of these genes does not completely remove the mannosylphosphates in N-glycans. This study was performed to find unknown key gene(s) involved in N-glycan mannosylphosphorylation in S. cerevisiae. For this purpose, each of one MNN4 and five MNN6 homologous genes were deleted from the och1Δmnn1Δmnn4Δmnn6Δ strain, which lacks yeast-specific hyper-mannosylation and the immunogenic α(1,3)-mannose structure. N-glycan profile analysis of cell wall mannoproteins and a secretory recombinant protein produced in mutants showed that the MNN14 gene, an MNN4 paralog with unknown function, is essential for N-glycan mannosylphosphorylation. Double disruption of MNN4 and MNN14 genes was enough to eliminate N-glycan mannosylphosphorylation. Our results suggest that the S. cerevisiae och1Δmnn1Δmnn4Δmnn14Δ strain, in which all yeast-specific N-glycan structures including mannosylphosphorylation are abolished, may have promise as a useful platform for glyco-engineering to produce therapeutic glycoproteins with human-compatible N-glycans.

  7. The Gaseous Phase as a Probe of the Astrophysical Solid Phase Chemistry

    NASA Astrophysics Data System (ADS)

    Abou Mrad, Ninette; Duvernay, Fabrice; Isnard, Robin; Chiavassa, Thierry; Danger, Grégoire

    2017-09-01

    In support of space missions and spectroscopic observations, laboratory experiments on ice analogs enable a better understanding of organic matter formation and evolution in astrophysical environments. Herein, we report the monitoring of the gaseous phase of processed astrophysical ice analogs to determine if the gaseous phase can elucidate the chemical mechanisms and dominant reaction pathways occurring in the solid ice subjected to vacuum ultra-violet (VUV) irradiation at low temperature and subsequently warmed. Simple (CH3OH), binary (H2O:CH3OH, CH3OH:NH3), and ternary ice analogs (H2O:CH3OH:NH3) were VUV-processed and warmed. The evolution of volatile organic compounds in the gaseous phase shows a direct link between their relative abundances in the gaseous phase, and the radical and thermal chemistries modifying the initial ice composition. The correlation between the gaseous and solid phases may play a crucial role in deciphering the organic composition of astrophysical objects. As an example, possible solid compositions of the comet Lovejoy are suggested using the abundances of organics in its comae.

  8. Analysis of the nucleus-encoded and chloroplast-targeted rieske protein by classic and site-directed mutagenesis of Chlamydomonas.

    PubMed Central

    de Vitry, C; Finazzi, G; Baymann, F; Kallas, T

    1999-01-01

    Three mutants of the alga Chlamydomonas reinhardtii affected in the nuclear PETC gene encoding the Rieske iron-sulfur protein 2Fe-2S subunit of the chloroplast cytochrome b(6)f complex have been characterized. One has a stable deletion that eliminates the protein; two others carry substitutions Y87D and W163R that result in low accumulation of the protein. Attenuated expression of the stromal protease ClpP increases accumulation and assembly into b(6)f complexes of the Y87D and W163R mutant Rieske proteins in quantities sufficient for analysis. Electron-transfer kinetics of these complexes were 10- to 20-fold slower than those for the wild type. The deletion mutant was used as a recipient for site-directed mutant petC alleles. Six glycine residues were replaced by alanine residues (6G6A) in the flexible hinge that is critical for domain movement; substitutions were created near the 2Fe-2S cluster (S128 and W163); and seven C-terminal residues were deleted (G171och). Although the 6G6A and G171och mutations affect highly conserved segments in the chloroplast Rieske protein, photosynthesis in the mutants was similar to that of the wild type. These results establish the basis for mutational analysis of the nuclear-encoded and chloroplast-targeted Rieske protein of photosynthesis. PMID:10521530

  9. Analysis of the nucleus-encoded and chloroplast-targeted rieske protein by classic and site-directed mutagenesis of Chlamydomonas.

    PubMed

    de Vitry, C; Finazzi, G; Baymann, F; Kallas, T

    1999-10-01

    Three mutants of the alga Chlamydomonas reinhardtii affected in the nuclear PETC gene encoding the Rieske iron-sulfur protein 2Fe-2S subunit of the chloroplast cytochrome b(6)f complex have been characterized. One has a stable deletion that eliminates the protein; two others carry substitutions Y87D and W163R that result in low accumulation of the protein. Attenuated expression of the stromal protease ClpP increases accumulation and assembly into b(6)f complexes of the Y87D and W163R mutant Rieske proteins in quantities sufficient for analysis. Electron-transfer kinetics of these complexes were 10- to 20-fold slower than those for the wild type. The deletion mutant was used as a recipient for site-directed mutant petC alleles. Six glycine residues were replaced by alanine residues (6G6A) in the flexible hinge that is critical for domain movement; substitutions were created near the 2Fe-2S cluster (S128 and W163); and seven C-terminal residues were deleted (G171och). Although the 6G6A and G171och mutations affect highly conserved segments in the chloroplast Rieske protein, photosynthesis in the mutants was similar to that of the wild type. These results establish the basis for mutational analysis of the nuclear-encoded and chloroplast-targeted Rieske protein of photosynthesis.

  10. Synthesis and characterizations of anion exchange organic-inorganic hybrid materials based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)

    SciTech Connect

    Zhang Shaoling; Wu Cuiming; Xu Tongwen . E-mail: twxu@ustc.edu.cn; Gong Ming; Xu Xiaolong

    2005-07-15

    A series of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid materials for anion exchange were prepared through sol-gel process of polymer precursors PPO-Si(OCH{sub 3}){sub 3}. PPO-Si(OCH{sub 3}){sub 3} were obtained from the reaction of bromomethylated PPO with 3-aminopropyl-trimethoxysilane (A1110). These polymer precursors then underwent hydrolysis and condensation with additional A1110 to generate hybrid materials. The reaction to produce polymer precursors was identified by FTIR; while FTIR, TGA, XRD, SEM, as well as conventional ion exchange capacity (IEC) measurements were conducted for the structures and properties of the prepared hybrids. TGA results show that this series of hybrid materials possess high thermal stability; XRD and SEM indicate that the prepared hybrid materials are amorphous and the inorganic and organic contents show good compatibility if the ratio between them is proper. The IEC values of the hybrid materials due to the amine groups range from 1.13 mmol/gBPPO (material i) to 4.80 mmol/gBPPO (material iv)

  11. 2-Methoxyphenyl isocyanate and 2-Methoxyphenyl isothiocyanate: conformers, vibration structure and multiplet Fermi resonance.

    PubMed

    Yenagi, Jayashree; Nandurkar, Anita R; Tonannavar, J

    2012-06-01

    IR and Raman spectral measurements in the region 3500-400/50 cm(-1) have been made for the liquid samples of 2-Methoxyphenyl isocyanate and 2-Methoxyphenyl isothiocyanate. A complete assignment of the measured bands has been proposed as aided by conformational and vibration analyses at B3LYP/6-311++G** level of calculations. Three conformers for 2-Methoxyphenyl isocyanate and two for 2-Methoxyphenyl isothiocyanate have been determined. The tilt of the isocyanate (NCO) and isothiocyanate (NCS) moieties with respect to phenyl ring are in broad agreement with their parents. Stretching mode frequencies of methyl group (-OCH(3)) in 2-Methoxyphenyl isocyanate have been lowered in the 2900-2800 cm(-1); deformation asymmetric modes are IR strong and symmetric one Raman strong. In 2-Methoxyphenyl isothiocyanate, a similar pattern is true for stretching modes but deformation asymmetric modes are IR strong and symmetric mode has not been observed. Multiplet absorption band system near 2200 cm(-1) in 2-Methoxyphenyl isocyanate has been interpreted to be caused by Fermi resonance. A similar pattern in absorption near 2100 cm(-1) in 2-Methoxyphenyl isothiocyanate but more complex Raman band pattern has also been explained through Fermi resonance from heuristic stand-point. Many Raman modes in 1300-1100 cm(-1) are intensified apparently owing to isothiocyanate than isocyanate moiety. Phenyl ring breathing mode is shifted to 1040 cm(-1) as strong Raman; the symmetric stretching mode of O-CH(3) near 1023 cm(-1) as strong absorption.

  12. Photo-fragmentation behavior of methyl- and methoxy-substituted derivatives of hexa-peri-hexabenzocoronene (HBC) cations

    NASA Astrophysics Data System (ADS)

    Zhen, Junfeng; Castellanos, Pablo; Linnartz, Harold; Tielens, Alexander G. G. M.

    2016-11-01

    A systematic study, using ion trap time-of-flight mass spectrometry, is presented for the photo-fragmentation of methyl- and methoxy-substituted derivatives of HBC cations, (OCH3)6HBC+ and (CH3)4(OCH3)2HBC+. Both substituted HBC cations fragment through sequential loss of CH3CO units upon laser (595nm) irradiation, resulting in a PAH-like derivative C36H12+ and a methyl-substituted PAH derivative C44H24+ , respectively. Upon ongoing irradiation, these species further fragment. For lower laser energy C44H24+ dehydrogenates and photo-fragments through CH3 and CHCH2 unit losses; for higher laser energy isomerization takes place, yielding a regular PAH-like configuration, and both stepwise dehydrogenation and C2/C2H2 loss pathways are found. C36H12+ follows largely this latter fragmentation scheme upon irradiation. It is concluded that the photo-dissociation mechanism of the substituted PAH cations studied here is site selective in the substituted subunit. This work also shows experimental evidence that photo-fragmentation of substituted PAHs may contribute to the formation in space of smaller species that are normally considered to form by merging atoms and molecules.

  13. The adsorption and reaction of ethylene glycol and 1,2-propanediol on Pd(111): A TPD and HREELS study

    NASA Astrophysics Data System (ADS)

    Griffin, Michael B.; Jorgensen, Erica L.; Medlin, J. Will

    2010-09-01

    The reactions of ethylene glycol and 1,2-propanediol have been studied on Pd(111) using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). Both molecules initially decompose through O-H activation, forming ethylenedioxy (-OCH 2CH 2O-) and 1,2-propanedioxy (-OCH 2CH(CH 3)O-) surface intermediates. For ethylene glycol, increases in thermal energy lead to dehydrogenation and formation of carbonyl species at both oxygen atoms. The resulting glyoxal (O═CHCH═O) either desorbs molecularly or reacts through one of two competing pathways. The favored pathway proceeds via C-C bond scission, dehydrogenation, and decarbonylation to form carbon monoxide and hydrogen. In a minor pathway, small amounts of glyoxal undergo C-O bond scission and recombination with surface hydrogen to form ethylene and water. The same reaction mechanism occurs for 1,2-propanediol after methyl elimination and formation of glyoxal. However, this is accompanied by a minor pathway involving a methylglyoxal (O=CHC(CH 3)=O) intermediate. The prevalence of the dehydrogenation/decarbonylation pathway in the current work is consistent with the high selectivity for C-C scission in the aqueous phase reforming of polyols on supported Pd catalysts.

  14. Intramolecular Oxidative O-Demethylation of an Oxoferryl Porphyrin Complexed with a Per-O-methylated β-Cyclodextrin Dimer.

    PubMed

    Kitagishi, Hiroaki; Kurosawa, Shun; Kano, Koji

    2016-11-22

    The intramolecular oxidation of ROCH3 to ROCH2 OH, where the latter compound spontaneously decomposed to ROH and HCHO, was observed during the reaction of the supramolecular complex (met-hemoCD3) with cumene hydroperoxide in aqueous solution. Met-hemoCD3 is composed of meso-tetrakis(4-sulfonatophenyl)porphinatoiron(III) (Fe(III) TPPS) and a per-O-methylated β-cyclodextrin dimer having an -OCH2 PyCH2 O- linker (Py=pyridine-3,5-diyl). The O=Fe(IV) TPPS complex was formed by the reaction of met-hemoCD3 with cumene hydroperoxide, and isolated by gel-filtration chromatography. Although the isolated O=Fe(IV) TPPS complex in the cyclodextrin cage was stable in aqueous solution at 25 °C, it was gradually converted to Fe(II) TPPS (t1/2 =7.6 h). This conversion was accompanied by oxidative O-demethylation of an OCH3 group in the cyclodextrin dimer. The results indicated that hydrogen abstraction by O=Fe(IV) TPPS from ROCH3 yields HO-Fe(III) TPPS and ROCH2(.) . This was followed by radical coupling to afford Fe(II) TPPS and ROCH2 OH. The hemiacetal (ROCH2 OH) immediately decomposed to ROH and HCHO. This study revealed the ability of oxoferryl porphyrin to induce two-electron oxidation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Study of the photon-induced formation and subsequent desorption of CH3OH and H2CO in interstellar ice analogs

    NASA Astrophysics Data System (ADS)

    Martín-Doménech, R.; Muñoz Caro, G. M.; Cruz-Díaz, G. A.

    2016-05-01

    Context. Methanol and formaldehyde are two simple organic molecules that are ubiquitously detected in the interstellar medium, in both the solid and gaseous phases. An origin in the solid phase and a subsequent nonthermal desorption into the gas phase is often invoked to explain their abundances in some of the environments where they are found. Experimental simulations under astrophysically relevant conditions have been carried out in the past four decades in order to find a suitable mechanism for that process. Aims: In particular, photodesorption from pure methanol ice (and presumably from pure formaldehyde ice) has been found to be negligible in previous works, probably because both molecules are very readily dissociated by vacuum-UV photons. Therefore, we explore the in situ formation and subsequent photon-induced desorption of these species, studying the UV photoprocessing of pure ethanol ice, and a more realistic binary H2O:CH4 ice analog. Methods: Experimental simulations were performed in an ultra-high vacuum chamber. Pure ethanol and binary H2O:CH4 ice samples deposited onto an infrared transparent window at 8 K were UV-irradiated using a microwave-discharged hydrogen flow lamp. Evidence of photochemical production of these two species and subsequent UV-photon-induced desorption into the gas phase were searched for by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer, respectively. After irradiation, ice samples were warmed up to room temperature until complete sublimation was attained for detection of volatile products. Results: Formation of CH3OH was only observed during photoprocessing of the H2O:CH4 ice analog, accounting for ~4% of the initial CH4 ice column density, but no photon-induced desorption was detected. Photochemical production of H2CO was observed in both series of experiments. Formation of formaldehyde accounted for ≤45% conversion of the initial ethanol ice, but it could not be quantified during

  16. The effect of a paramagnetic metal ion within a molecule: comparison of the structurally identical paramagnetic [3,3-Fe(1,2-C2B9H11)2]- with the diamagnetic [3,3-Co(1,2-C2B9H11)2]- sandwich complexes.

    PubMed

    Cioran, Ana M; Teixidor, Francesc; Viñas, Clara

    2015-02-14

    Derivatives of the ferrabisdicarbollide [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-) have been produced starting from the zwitterion [3,3'-Fe(8-(OCH(2)CH(2))(2)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))], 1, upon reaction with nucleophiles: alkoxides, halides and hydrosulfide ions HS(-). The result has been the preparation of [3,3'-Fe(8-(OCH(2)CH(2))(2)R/X-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] (R = OMe, [2](-); OEt, [3](-); OCH(2)CH(2)OCH(3), [4](-); and X = Cl, [5](-); Br, [6](-); I, [7](-); and SH, [8](-)). The reaction behavior of is comparable to the well-studied cobalt equivalent, [3,3'-Co(8-(OCH(2)CH(2))2-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))], and the yields and stability of the resulting complexes are similar. These results are relevant taking into account that [3,3'-Fe(1,2-C(2)B(9)H(11))(2))(-) is a paramagnetic anion. Implications of this are observed in the (11)B-, (1)H and (13)C NMR spectra of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) and [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-) that having identical sandwich molecular structures and the same negative charge have absolutely different widths of the NMR field, between 15 and -25 ppm for [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) and in the range 150 to -550 ppm for [3,3'-Fe(1,2-C(2)B(9)H(11))(2)](-). The sharpness of both spectra is on the other hand comparable, although no B-H couplings are observed in the Fe metallacarborane or its derivatives. Remarkable is the comparative influence vs. [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) of replacing Co by Fe on the elements of the cluster layer nearest to the metal. The two equivalent C cluster (Cc) atoms are influenced at 36 840 Hz, the two equivalent B atoms that are adjacent to the two Cc are influenced at 38 157 Hz and the single B that is adjacent to the two B atoms is influenced at 44 062 Hz. Remarkable is the similar influence on B and on C, taking into account that the values have been obtained from two distinct NMR spectra of (11)B and (13)C. The {(11)B-(11)B} COSY NMR and {(1)H

  17. Trifunctional metal ion-catalyzed solvolysis: Cu(II)-promoted methanolysis of N,N-bis(2-picolyl) benzamides involves unusual Lewis acid activation of substrate, delivery of coordinated nucleophile, powerful assistance of the leaving group departure.

    PubMed

    Raycroft, Mark A R; Maxwell, Christopher I; Oldham, Robyn A A; Andrea, Areen Saffouri; Neverov, Alexei A; Brown, R Stan

    2012-10-01

    The methanolyses of Cu(II) complexes of a series of N,N-bis(2-picolyl) benzamides (4a-g) bearing substituents X on the aromatic ring were studied under (s)(s)pH-controlled conditions at 25 °C. The active form of the complexes at neutral (s)(s)pH has a stoichiometry of 4:Cu(II):((-)OCH(3))(HOCH(3)) and decomposes unimolecularly with a rate constant k(x). A Hammett plot of log(k(x)) vs σ(x) values has a ρ(x) of 0.80 ± 0.05. Solvent deuterium kinetic isotope effects of 1.12 and 1.20 were determined for decomposition of the 4-nitro and 4-methoxy derivatives, 4b:Cu(II):((-)OCH(3))(HOCH(3)) and 4g:Cu(II):((-)OCH(3))(HOCH(3)), in the plateau region of the (s)(s)pH/log(k(x)) profiles in both CH(3)OH and CH(3)OD. Activation parameters for decomposition of these complexes are ΔH(++) = 19.1 and 21.3 kcal mol(-1) respectively and ΔS(++) = -5.1 and -2 cal K(-1) mol(-1). Density functional theory (DFT) calculations for the reactions of the Cu(II):((-)OCH(3))(HOCH(3)) complexes of 4a,b and g (4a, X = 3,5-dinitro) were conducted to probe the relative transition state energies and geometries of the different states. The experimental and computational data support a mechanism where the metal ion is coordinated to the N,N-bis(2-picolyl) amide unit and positioned so that it permits delivery of a coordinated Cu(II):((-)OCH(3)) nucleophile to the C═O in the rate-limiting transition state (TS) of the reaction. This proceeds to a tetrahedral intermediate INT, occupying a shallow minimum on the free energy surface with the Cu(II) coordinated to both the methoxide and the amidic N. Breakdown of INT is a virtually barrierless process, involving a Cu(II)-assisted departure of the bis(2-picolyl)amide anion. The analysis of the data points to a trifunctional role for the metal ion in the solvolysis mechanism where it activates intramolecular nucleophilic attack on the C═O group by coordination to an amidic N in the first step of the reaction and subsequently assists leaving group

  18. A theoretical study on the hydrogen-bonding interactions between flavonoids and ethanol/water.

    PubMed

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui

    2016-04-01

    Ethanol and water are the solvents most commonly used to extract flavonoids from propolis. Do hydrogen-bonding interactions exist between flavonoids and ethanol/water? In this work, this question was addressed by using density functional theory (DFT) to provide information on the hydrogen-bonding interactions between flavonoids and ethanol/water. Chrysin and Galangin were chosen as the representative flavonoids. The investigated complexes included chrysin-H2O, chrysin-CH3CH2OH, galangin-H2O and galangin-CH3CH2OH dyads. Molecular geometries, hydrogen-bond binding energies, charges of monomers and dyads, and topological analysis were studied at the B3LYP/M062X level of theory with the 6-31++G(d,p) basis set. The main conclusions were: (1) nine and ten optimized hydrogen-bond geometries were obtained for chrysin-H2O/CH3CH2OH and galangin-H2O/CH3CH2OH complexes, respectively. (2) The hydrogen atoms except aromatic H1 and H5 and all of the oxygen atoms can form hydrogen-bonds with H2O and CH3CH2OH. Ethanol and water form strong hydrogen-bonds with the hydroxyl, carbonyl and ether groups in chrysin/galangin and form weak hydrogen-bonds with aromatic hydrogen atoms. Except in structures labeled A and B, chrysin and galangin interact more strongly with H2O than CH3CH2OH. (3) When chrysin and galangin form hydrogen-bonds with H2O and CH3CH2OH, charge transfers from the hydrogen-bond acceptor (H2O and CH3CH2OH in structures A, B, G, H, I, J) to the hydrogen-bond donor (chrysin and galangin in structure A, B, G, H, I, J). The stronger hydrogen-bond makes the hydrogen-bond donor lose more charge (A> B> G> H> I> J). (4) Most of the hydrogen-bonds in chrysin/galangin-H2O/CH3CH2OH complexes may be considered as electrostatic dominant, while C-O2···H in structures labeled E and C-O5···H in structures labeled J are hydrogen-bonds combined of electrostatic and covalent characters. H9, H7, and O4 are the preferred hydrogen-bonding sites.

  19. Theoretical study of the stabilities and detonation performance of 5-nitro-3-trinitromethyl-1H-1,2,4-triazole and its derivatives.

    PubMed

    Zhang, Xueli; Gong, Xuedong

    2015-02-01

    5-Nitro-3-trinitromethyl-1H-1,2,4-triazole (NTMT, A) and its substituted derivatives A-CH3, A-OCH3, A-NH2, A-OH, A-NO2, and A-ONO2 were studied using density functional theory (DFT). For all of the molecules except for A-ONO2, the C-NO2 bond in the trinitromethyl group was found to be the weakest, and no transition state occurred during the scission of this bond. The weakest C-NO2 of the trinitromethyl group bond dissociation energies for all of the molecules were all very similar. Most of the title molecules had similar frontier orbital distributions and comparable energy gaps between the frontier orbitals. The impact sensitivity (h 50, in cm), predicted at various levels of theory, decreased in the order A-NH2 (53.0-71.0) > A-CH3 (53.0) > A (36.7) > A-OCH3 (32.6-42.3) > A-OH (26.7-53.0) > A-NO2 (5.6-7.4) > A-ONO2 (4.6-6.1). Their detonation velocities (D), detonation pressures (P), and specific impulses (I s) were 8.02-8.82 km/s, 29.92-35.54 GPa, and 214-260 s, respectively. Composite explosives made from hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and A, A-OH, A-NH2, A-NO2, or A-ONO2 as an oxidizer were found to possess much better detonation performance (D = 9.04-9.29 km/s, P = 37.25-39.26 GPa, and I s = 270-281 s). Thus, introducing -OCH3, -OH, and -NH2 groups into A produced new explosives with acceptable stability and good detonation performance. A-OH and A-NH2 appear to be promising candidates for oxidizers in composite explosives.

  20. Thermal Decomposition Mechanisms of Lignin Model Compounds: From Phenol to Vanillin

    NASA Astrophysics Data System (ADS)

    Scheer, Adam Michael

    Lignin is a complex, aromatic polymer abundant in cellulosic biomass (trees, switchgrass etc.). Thermochemical breakdown of lignin for liquid fuel production results in undesirable polycyclic aromatic hydrocarbons that lead to tar and soot byproducts. The fundamental chemistry governing these processes is not well understood. We have studied the unimolecular thermal decomposition mechanisms of aromatic lignin model compounds using a miniature SiC tubular reactor. Products are detected and characterized using time-of-flight mass spectrometry with both single photon (118.2 nm; 10.487 eV) and 1 + 1 resonance-enhanced multiphoton ionization (REMPI) as well as matrix isolation infrared spectroscopy. Gas exiting the heated reactor (300 K--1600 K) is subject to a free expansion after a residence time of approximately 100 micros. The expansion into vacuum rapidly cools the gas mixture and allows the detection of radicals and other highly reactive intermediates. By understanding the unimolecular fragmentation patterns of phenol (C6H5OH), anisole (C6H 5OCH3) and benzaldehyde (C6H5CHO), the more complicated thermocracking processes of the catechols (HO-C 6H4-OH), methoxyphenols (HO-C6H4-OCH 3) and hydroxybenzaldehydes (HO-C6H4-CHO) can be interpreted. These studies have resulted in a predictive model that allows the interpretation of vanillin, a complex phenolic ether containing methoxy, hydroxy and aldehyde functional groups. This model will serve as a guide for the pyrolyses of larger systems including lignin monomers such as coniferyl alcohol. The pyrolysis mechanisms of the dimethoxybenzenes (H3C-C 6H4-OCH3) and syringol, a hydroxydimethoxybenzene have also been studied. These results will aid in the understanding of the thermal fragmentation of sinapyl alcohol, the most complex lignin monomer. In addition to the model compound work, pyrolyisis of biomass has been studied via the pulsed laser ablation of poplar wood. With the REMPI scheme, aromatic lignin decomposition

  1. Bismuthπ arene versus bismuthhalide coordination in heterocyclic diorganobismuth(iii) compounds with transannular N→Bi interaction.

    PubMed

    Toma, Ana Maria; Pop, Alexandra; Silvestru, Anca; Rüffer, Tobias; Lang, Heinrich; Mehring, Michael

    2017-03-21

    New diorganobismuth(iii) bromides of type [RN(CH2C6H4)2]BiBr [R = C6H5CH2 (1), C6H5CH2CH2 (2), and CH3OCH2CH2 (3)], based on the heterocyclic butterfly-like tetrahydro-dibenzo[c,f][1,5]azabismocine framework, were prepared starting from the corresponding RN(CH2C6H4Br-2)2 in a succession of reactions including ortho-lithiation and treatment of the dilithio derivative with BiBr3 in a 1 : 1 molar ratio. Further exchange reactions between bromides and appropriate metal halides or ammonium fluoride resulted in the formation of [RN(CH2C6H4)2]BiX [X = Cl and I for R = C6H5CH2 (4 and 5) and C6H5CH2CH2 (6 and 7) and X = F (8), Cl (9), and I (10) for R = CH3OCH2CH2]. All ten compounds were structurally characterized in solution by NMR and in the solid state by single-crystal X-ray diffraction. Strong transannular N→Bi interactions were observed in all the investigated diorganobismuth(iii) halides, thus giving rise to hypervalent 10-Bi-4 species in 1, 2, 4-7 and 12-Bi-5 species in 3, 8-10, where the oxygen atom in the pendant arm is intramolecularly coordinated to bismuth. The molecules are associated in dimeric units by strong Biπ arene interactions in 3, 4, and 10 (approx. 3.50 Å) and by BiX interactions in 1, 5, and 7. Bromide 1, chloride 4, and iodide 5 are isostructural, but stronger polarization of the Bi-Cl bond favors Biπ arene interaction in 4 over Bihalide interactions, as observed in 1 and 5. In the isostructural series [RN(CH2C6H4)2]BiX (R = CH3OCH2CH2), Bioxygen interactions compensate the electron deficiency at bismuth in fluoride 8 and chloride 9, whereas the coordination sphere of bismuth is completed by a combination of Biπ arene and Bihalide interactions in bromide 3 and only by Biπ arene interactions in iodide 10. Moreover, weak Hπ arene and HX intermolecular interactions, mainly of dispersion type, contribute to supramolecular networks in all three series of compounds.

  2. Electronic Absorption Spectra and Phosphorescence of Oxygen-Containing Molybdenum(IV) Complexes.

    PubMed

    Isovitsch, Ralph A.; Beadle, A. Scott; Fronczek, Frank R.; Maverick, Andrew W.

    1998-08-24

    Electronic absorption and emission spectra are reported for salts of two oxomolybdenum(IV) cations, [MoOCl(CN-t-Bu)(4)](+) and [MoOCl(Ph(2)PCH(2)CH(2)PPh(2))(2)](+), and for the new Mo(IV) complex [trans-Mo(OCH(3))(2)(CN-t-Bu)(4)](2+). All three ions show absorption bands (lambda(max,abs) 550-570 nm; epsilon 45-120 M(-)(1) cm(-)(1)) attributable to the (1)A(1)[(d(xy)())(2)] --> (1)E[(d(xy)())(1)(d(xz)()(,)(yz)())(1)] (C(4)(v)()) transition, and the last two show weak shoulders in the 700-750 nm range due to the analogous spin-forbidden ((1)A(1) --> (3)E) transition. Phosphorescence (lambda(max,em) 850-960 nm) occurs in the solid state for all three compounds at both room temperature and 77 K, and for [MoOCl(CN-t-Bu)(4)](+) in CH(2)Cl(2) at room temperature. These are the first phosphorescences recorded for molybdenum(IV) complexes. [MoOCl(CN-t-Bu)(4)](BPh(4)) precipitates quickly if NaBPh(4) is added to the Mo(IV) solution prepared from MoCl(5) and tert-butyl isocyanide in CH(3)OH. However, if NaPF(6) is used instead, [trans-Mo(OCH(3))(2)(CN-t-Bu)(4)](PF(6))(2) (formed by reaction of [MoOCl(CN-t-Bu)(4)](+) with methanol) crystallizes over a period of ca. 24 h. The crystal structure of [trans-Mo(OCH(3))(2)(CN-t-Bu)(4)](PF(6))(2) has been determined: C(22)H(42)F(12)MoN(4)O(2)P(2), monoclinic; space group P2(1)/c; a = 9.1538(8) Å, b = 15.709(2) Å, c = 13.456(2) Å; beta = 103.31(1) degrees; Z = 2; R(F) = 0.063, R(w)(F) = 0.056 for 2719 reflections with I > sigma(I).

  3. Redox-induced terpyridyl substitution in the Os(VI)-hydrazido complex, trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+).

    PubMed

    Huynh, M H; Lee, D G; White, P S; Meyer, T J

    2001-07-30

    Reaction between the Os(VI)-hydrazido complex, trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+) (tpy = 2,2':6',2"-terpyridine and O(CH(2))(4)N(-) = morpholide), and a series of N- or O-bases gives as products the substituted Os(VI)-hydrazido complexes, trans-[Os(VI)(4'-RNtpy)(Cl)(2)(NN(CH(2))(4)O)](2+) or trans-[Os(VI)(4'-ROtpy)(Cl)(2)(NN(CH(2))(4)O)](2+) (RN(-) = anilide (PhNH(-)); S,S-diphenyl sulfilimide (Ph(2)S=N(-)); benzophenone imide (Ph(2)C=N(-)); piperidide ((CH(2))(5)N(-)); morpholide (O(CH(2))(4)N(-)); ethylamide (EtNH(-)); diethylamide (Et(2)N(-)); and tert-butylamide (t-BuNH(-)) and RO(-) = tert-butoxide (t-BuO(-)) and acetate (MeCO(2)(-)). The rate law for the formation of the morpholide-substituted complex is first order in trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+) and second order in morpholine with k(morp)(25 degrees C, CH(3)CN) = (2.15 +/- 0.04) x 10(6) M(-)(2) s(-)(1). Possible mechanisms are proposed for substitution at the 4'-position of the tpy ligand by the added nucleophiles. The key features of the suggested mechanisms are the extraordinary electron withdrawing effect of Os(VI) on tpy and the ability of the metal to undergo intramolecular Os(VI) to Os(IV) electron transfer. These substituted Os(VI)-hydrazido complexes can be electrochemically reduced to the corresponding Os(V), Os(IV), and Os(III) forms. The Os-N bond length of 1.778(4) A and Os-N-N angle of 172.5(4) degrees in trans-[Os(VI)(4'-O(CH(2))(4)Ntpy)(Cl)(2)(NN(CH(2))(4)O)](2+) are consistent with sp-hybridization of the alpha-nitrogen of the hydrazido ligand and an Os-N triple bond. The extensive ring substitution chemistry implied for the Os(VI)-hydrazido complexes is discussed.

  4. High temperature shock tube studies on the thermal decomposition of O3 and the reaction of dimethyl carbonate with O-atoms.

    PubMed

    Peukert, S L; Sivaramakrishnan, R; Michael, J V

    2013-05-09

    The shock tube technique was used to study the thermal decomposition of ozone, O3, with a view to using this as a thermal precursor of O-atoms at high temperatures. The formation of O-atoms was measured behind reflected shock waves by using atomic resonance absorption spectrometry (ARAS). The experiments span a T-range, 819 K ≤ T ≤ 1166 K, at pressures 0.13 bar ≤ P ≤ 0.6 bar. Unimolecular rate theory provides an excellent representation of the falloff characteristics from the present and literature data on ozone decomposition at high temperatures. The present decomposition study on ozone permits its usage as a thermal source for O-atoms allowing measurements for, O + CH3OC(O)OCH3 → OH + CH3OC(O)OCH2 [A]. Reflected shock tube experiments monitoring the formation and decay of O-atoms were performed on reaction A using mixtures of O3 and CH3OC(O)OCH3, (DMC), in Kr bath gas over the T-range, 862 K ≤ T ≤ 1167 K, and pressure range, 0.15 bar ≤ P ≤ 0.33 bar. A detailed model was used to fit the O-atom temporal profile to obtain experimental rate constants for reaction A. Rate constants from the present experiments for O + DMC can be represented by the Arrhenius expression: kA(T) = 2.70 × 10(-11) exp(-2725 K/T) cm(3) molecule(-1) s(-1) (862-1167 K). Transition state theory calculations employing CCSD(T)/cc-pv∞z//M06-2X/cc-pvtz energetics and molecular properties for reaction A are in good agreement with the experimental rate constants. The theoretical rate constants can be well represented (to within ±10%) over the 500-2000 K temperature range by: kA(T) = 1.87 × 10(-20)T(2.924) exp(-2338 K/T) cm(3) molecule(-1) s(-1). The present study represents the first experimental measurement and theoretical study on this bimolecular reaction which is of relevance to the high temperature oxidation of DMC.

  5. Searching for trans ethyl methyl ether in Orion KL⋆

    NASA Astrophysics Data System (ADS)

    Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

    2015-10-01

    We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm-2 and ≤(1.0 ± 0.2) × 1015 cm-2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. This work was also based on observations carried out with the IRAM 30-m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).Appendix A is available in electronic form at http://www.aanda.org

  6. Polyethylene oxide surfaces of variable chain density by chemisorption of PEO-thiol on gold: adsorption of proteins from plasma studied by radiolabelling and immunoblotting.

    PubMed

    Unsworth, Larry D; Sheardown, Heather; Brash, John L

    2005-10-01

    The mechanisms involved in the inhibition of protein adsorption by polyethylene oxide (PEO) are not completely understood, but it is believed that PEO chain length, chain density and chain conformation all play a role. In this work, surfaces formed by chemisorption of PEO-thiol to gold were investigated: the effects of PEO chain density, chain length (600, 750, 2000 and 5000 MW) and end-group (-OH, -OCH3) on protein adsorption from plasma are reported. Similar to previous single protein adsorption studies (L.D. Unsworth et al., Langmuir 2005;21:1036-41) it was found that, of the different surfaces investigated, PEO layers formed from solutions near the cloud point adsorbed the lowest amount of fibrinogen from plasma. Layers of hydroxyl-terminated PEO of MW 600 formed under these low solubility conditions showed almost complete suppression (versus controls) of the Vroman effect, with 20+/-1 ng/cm2 adsorbed fibrinogen at the Vroman peak and 6.7+/-0.6 ng/cm2 at higher plasma concentration. By comparison, Vroman peak adsorption was 70+/-20 and 50+/-3 ng/cm2, respectively, for 750-OCH3 and 2000-OCH3 layers formed under low solubility conditions; adsorption on these surfaces at higher plasma concentration was 16+/-9 and 12+/-3 ng/cm2. Thus in addition to the effect of solution conditions noted previously, the results of this study also suggest a chain end group effect which inhibits fibrinogen adsorption to, and/or facilitates displacement from, hydroxyl terminated PEO layers. Fibrinogen adsorption from plasma was not significantly different for surfaces prepared with PEO of molecular weight 750 and 2000 when the chain density was the same ( approximately 0.5 chains/nm2) supporting the conclusion that chain density may be the key property for suppression of protein adsorption. The proteins eluted from the surfaces after contact with plasma were investigated by SDS-PAGE and immunoblotting. A number of proteins were detected on the various surfaces including fibrinogen

  7. Candida albicans mannans mediate Streptococcus mutans exoenzyme GtfB binding to modulate cross-kingdom biofilm development in vivo

    PubMed Central

    Liu, Yuan; Kim, Dongyeop; Li, Yong; Krysan, Damian J.

    2017-01-01

    Candida albicans is frequently detected with heavy infection by Streptococcus mutans in plaque-biofilms from children with early-childhood caries (ECC). This cross-kingdom biofilm contains an extensive matrix of extracellular α-glucans that is produced by an exoenzyme (GtfB) secreted by S. mutans. Here, we report that mannans located on the outer surface of C. albicans cell-wall mediates GtfB binding, enhancing glucan-matrix production and modulating bacterial-fungal association within biofilms formed in vivo. Using single-molecule atomic force microscopy, we determined that GtfB binds with remarkable affinity to mannans and to the C. albicans surface, forming a highly stable and strong bond (1–2 nN). However, GtfB binding properties to C. albicans was compromised in strains defective in O-mannan (pmt4ΔΔ) or N-mannan outer chain (och1ΔΔ). In particular, the binding strength of GtfB on och1ΔΔ strain was severely disrupted (>3-fold reduction vs. parental strain). In turn, the GtfB amount on the fungal surface was significantly reduced, and the ability of C. albicans mutant strains to develop mixed-species biofilms with S. mutans was impaired. This phenotype was independent of hyphae or established fungal-biofilm regulators (EFG1, BCR1). Notably, the mechanical stability of the defective biofilms was weakened, resulting in near complete biomass removal by shear forces. In addition, these in vitro findings were confirmed in vivo using a rodent biofilm model. Specifically, we observed that C. albicans och1ΔΔ was unable to form cross-kingdom biofilms on the tooth surface of rats co-infected with S. mutans. Likewise, co-infection with S. mutans defective in GtfB was also incapable of forming mixed-species biofilms. Taken together, the data support a mechanism whereby S. mutans-secreted GtfB binds to the mannan layer of C. albicans to promote extracellular matrix formation and their co-existence within biofilms. Enhanced understanding of Gtf

  8. Reaction mechanism of ethylene glycol decomposition on Pt model catalysts: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Lv, Cun-Qin; Yang, Bo; Pang, Xian-Yong; Wang, Gui-Chang

    2016-12-01

    Understanding and controlling bond beak sequence is important in catalytic processes. The DFT-GGA method combined with slab model was performed to study the ethylene glycol decomposition on various Pt model catalysts such as close-packed Pt(111), stepped Pt(211) and a more open one, Pt(100). Calculation results show that the adsorption energies of ethylene glycol and other decomposition species depend on the coordination number of surface atom, that is, low coordination number correspond to high adsorption energy. Moreover, it was found that final products of ethylene glycol decomposition are CO and H2 on all model catalysts, but the reaction mechanism varies: On Pt(111), the first step is Osbnd H bond scission, followed by Csbnd H bond cleavage, namely C2H6O2 → HOCH2CH2O + H → HOCH2CHO + 2H→ HOCH2CO +3H → OCH2CO + 4H → OCHCO + 5H → CO + HCO + 5H → 2CO + 6H→ 2CO + 3H2; On Pt(211) and Pt(100), however, it is a second Osbnd H bond cleavage that follows the initial Osbnd H bond scission, that is, C2H6O2 → HOCH2CH2O + H → OCH2CH2O + 2H → OCHCH2O + 3H → OCHCHO + 4H → 2HCO + 4H → 2CO + 6H → 2CO + 3H2 on Pt(211), and C2H6O2 →HOCH2CH2O+ H → OCH2CH2O + 2H→OCHCH2O+3H→OCCH2O+4H→CO+H2CO+4H→CO+HCO+5H→2CO+6H→2CO+3H2 on Pt(100) For the catalytic order of ethylene glycol to form H2, it may be determined based on the rate-controlling step, and it is Pt(111) > Pt(211) > Pt(100).

  9. Homogeneous solvation controlled photoreduction of cobalt(III) complexes in aqueous 2-methyl-2-propanol solutions. Linear solvation energy relationship and cyclic voltammetric analyses

    NASA Astrophysics Data System (ADS)

    Anbalagan, K.; Lydia, I. Sharmila

    2008-03-01

    The effect of solvent participation on the ligand-to-metal charge transfer (LMCT, L → Co III) reduction of the of Co III(en) 2Br(RC 6H 4NH 2) 2+ where R = m-OCH 3, p-F, H, m-CH 3, p-CH 3,p-OC 2H 5 and p-OCH 3 were examined in aqueous 2-methyl-2-propanol (Bu tOH) solutions. The change in the reduction behavior of Co III centre was also examined through cyclic voltammetric studies. The observed reduction in quantum yield due to LMCT excitation can mainly be accounted using linear solvation energy relationship (LSER) comprising model correlation equations. These consist of empirical parameters such as Grunwald-Winstein's solvent ionizing power, Y, Dimroth-Richardt's solvent micro-polarity parameter, ETN, Gutmann's donor number, DN N, along with Kamlet-Taft's solvatochromic parameters (hydrogen bond acceptor acidity/basicity α/ β and solvent dipolarity/polarizability, π*). The origin of solvent effect is found to be due to microscopic interaction between the solvent donor and the nitrogen-bound hydrogen of the ligand. Cyclic voltammograms show an irreversible reduction of Co III in DMF using Glassy Carbon Electrode, GCE, the redox peaks for the aniline complexes appear at -0.20 and 0.525 V. Irradiation of the complexes with UV light ( λ = 254 nm) in binary mixtures produce Co IIaq and the concentration of this species are highly dependent on xalc ( xalc = mole fraction of alcohol). The observed quantum yield (log ΦCo(II)) is found to be linearly related to mole fraction of organic co-solvent added in the mixture, therefore, log ΦCo(II) = 26.41 × 10 -2 when x2 = 0.0094 and 43.75 × 10 -2 when x2 = 0.076 for a typical complex Co III(en) 2Br( p-OCH 3C 6H 4NH 2) 2+ in aqueous 2-methyl-2-propanol at 300 K. Cyclic voltammetry and LSER analyses illustrate the variation of reduction property of Co(III) by the aryl ligand and homogeneous solvation of the excited state of the complex Co III(en) 2Br(RC 6H 4NH 2) 2+ in H 2O/Bu tOH mixtures.

  10. A tray-shaped, Pd(II)-clipped Au₃ complex as a scaffold for the modular assembly of [3×n] Au ion clusters.

    PubMed

    Osuga, Takafumi; Murase, Takashi; Hoshino, Manabu; Fujita, Makoto

    2014-10-13

    A tray-shaped Pd(II)3Au(I)3 complex (1) is prepared from 3,5-bis(3-pyridyl)pyrazole by means of tricyclization with Au(I) followed by Pd(II) clipping. Tray 1 is an efficient scaffold for the modular assembly of [3×n] Au(I) clusters. Treatment of 1 with the Au(I)3 tricyclic guest 2 in H2O/CH3CN (7:3) or H2O results in the selective formation of a [3×2] cluster (1⋅2) or a [3×3] cluster (1⋅2⋅1), respectively. Upon subsequent addition of Ag(I) ions, these complexes are converted to an unprecedented Au3-Au3-Ag-Au3-Au3 metal ion cluster. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2C(O)OH2+

    NASA Astrophysics Data System (ADS)

    Lee, Richard; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    2006-09-01

    Previous studies have shown that the solitary ketene-water ion CH2C(O)OH2+ (1) does not isomerize into CH2C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2O loss from low-energy 1,3-dihydroxyacetone ions (HOCH2)2CO+. A mechanistic analysis using the CBS-QB3 model chemistry shows that such molecular ions rearrange into hydrogen-bridged radical cations [CH2C(O)O(H)-H...OCH2]+ in which the CH2O molecule catalyzes the transformation 1 --> 2 prior to dissociation. The barrier for the unassisted reaction, 29 kcal mol-1, is reduced to a mere 0.6 kcal mol-1 for the catalysed transformation. Formaldehyde is an efficient catalyst because its proton affinity meets the criterion for facile proton-transport catalysis.

  12. On the physical nature of halogen bonds: a QTAIM study.

    PubMed

    Syzgantseva, Olga A; Tognetti, Vincent; Joubert, Laurent

    2013-09-12

    In this article, we report a detailed study on halogen bonds in complexes of CHCBr, CHCCl, CH2CHBr, FBr, FCl, and ClBr with a set of Lewis bases (NH3, OH2, SH2, OCH2, OH(-), Br(-)). To obtain insight into the physical nature of these bonds, we extensively used Bader's Quantum Theory of Atoms-in-Molecules (QTAIM). With this aim, in addition to the examination of the bond critical points properties, we apply Pendás' Interacting Quantum Atoms (IQA) scheme, which enables rigorous and physical study of each interaction at work in the formation of the halogen-bonded complexes. In particular, the influence of primary and secondary interactions on the stability of the complexes is analyzed, and the roles of electrostatics and exchange are notably discussed and compared. Finally, relationships between QTAIM descriptors and binding energies are inspected.

  13. Laboratory simulation of the photoprocessing and warm-up of cometary and pre-cometary ices - Production and analysis of complex organic molecules

    NASA Technical Reports Server (NTRS)

    Schutte, W. A.; Allamandola, L. J.; Sandford, S. A.

    1992-01-01

    The recent missions to Comet Halley detected large quantities of organic material on grains as well as organic molecules in the gas phase. A possible origin of these materials is the energetic processing of ice mantles on the grains prior to comet formation, either in the pre-solar nebula or the interstellar medium. This process was simulated in the laboratory by depositing interstellar ice analogs (H2O/CH3OH/CO/NH3) on a cold (10 K) substrate with simultaneous UV irradiation. The material evaporating during warm-up of the photolyzed ice as well as the residue remaining at room temperature was analyzed by a number of techniques. It was found that a large number of organic molecules of various complexity are synthesized during the simulation process, stressing the possible significance of UV photolysis for producing the organic Comet material.

  14. Thermodynamic properties (enthalpy, bond energy, entropy, and heat capacity) and internal rotor potentials of vinyl alcohol, methyl vinyl ether, and their corresponding radicals.

    PubMed

    da Silva, Gabriel; Kim, Chol-Han; Bozzelli, Joseph W

    2006-06-29

    Vinyl alcohols (enols) have been discovered as important intermediates and products in the oxidation and combustion of hydrocarbons, while methyl vinyl ethers are also thought to occur as important combustion intermediates. Vinyl alcohol has been detected in interstellar media, while poly(vinyl alcohol) and poly(methyl vinyl ether) are common polymers. The thermochemical property data on these vinyl alcohols and methyl vinyl ethers is important for understanding their stability, reaction paths, and kinetics in atmospheric and thermal hydrocarbon-oxygen systems. Enthalpies , entropies , and heat capacities (C(p)()(T)) are determined for CH(2)=CHOH, C(*)H=CHOH, CH(2)=C(*)OH, CH(2)=CHOCH(3), C(*)H=CHOCH(3), CH(2)=C(*)OCH(3), and CH(2)=CHOC(*)H(2). Molecular structures, vibrational frequencies, , and C(p)(T) are calculated at the B3LYP/6-31G(d,p) density functional calculation level. Enthalpies are also determined using the composite CBS-Q, CBS-APNO, and G3 methods using isodesmic work reactions to minimize calculation errors. Potential barriers for internal rotors are calculated at the B3LYP/6-31G(d,p) level and used to determine the hindered internal rotational contributions to entropy and heat capacity. The recommended ideal gas phase values calculated in this study are the following (in kcal mol(-1)): -30.0, -28.9 (syn, anti) for CH(2)=CHOH; -25.6, -23.9 for CH(2)=CHOCH(3); 31.3, 33.5 for C(*)H=CHOH; 27.1 for anti-CH(2)=C(*)OH; 35.6, 39.3 for C(*)H=CHOCH(3); 33.5, 32.2 for CH(2)=C(*)OCH(3); 21.3, 22.0 for CH(2)=CHOC(*)H(2). Bond dissociation energies (BDEs) and group additivity contributions are also determined. The BDEs reveal that the O-H, O-CH(3), C-OH, and C-OCH(3) bonds in vinyl alcohol and methyl vinyl ether are similar in energy to those in the aromatic molecules phenol and methyl phenyl ether, being on average around 3 kcal mol(-1) weaker in the vinyl systems. The keto-enol tautomerization enthalpy for the interconversion of vinyl alcohol to acetaldehyde is

  15. Preparative separation of glycoalkaloids α-solanine and α-chaconine by centrifugal partition chromatography.

    PubMed

    Attoumbré, Jacques; Lesur, David; Giordanengo, Philippe; Baltora-Rosset, Sylvie

    2012-11-01

    The main glycoalkaloids of a commercial potato cultivar, α-chaconine and α-solanine, were extracted from sprouts of Solanum tuberosum cv. Pompadour by a mixture of MeOH/H(2)O/CH(3)COOH (400/100/50, v/v/v). In these conditions, 2.8±0.62g of crude extract were obtained from 50g of fresh sprouts and the total glycoalkaloid content was determined by analytical HPLC at 216.5mg/100g. α-Chaconine and α-solanine were separated in a preparative scale using centrifugal partition chromatography (CPC). In a solvent system composed of a mixture of ethyl acetate/butanol/water (15/35/50, v/v/v), α-chaconine (54mg) and α-solanine (15mg) were successfully isolated from the crude extract in one step of purification. The purity of isolated compounds was determined to be higher than 92% by HPLC analysis.

  16. Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

    DOEpatents

    Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

    2001-01-01

    Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

  17. Photochemistry of Surface-Confined Mononuclear and Trinuclear Ruthenium Carbonyl Complexes. Direct Evidence for the Ability to Isolate Photogenerated Intermediates from each other on High Surface Area Silica.

    DTIC Science & Technology

    1982-01-04

    foned: [S -LRu(C0) 4 under 355 nm + 20 nm irradiation yields [S-LRu(CO) 3L’ (L’ = 13CO, PPh 3, P(OCH 2)3CCH 2CH3) when suspended in isooctane ...UUTY CLASSIVICATIO4 OF THIS PAGtI[(Wh- 000m ZrL-e0m - L’ [S4-L3Ru,(CO)g, suspended in isooctane , yields [S -LRu(CO)d when irradiated at 436 nm uner...erate [S.-L Ru (CO)g when isooctane solutions are purged with N2 to remove CO.The [S+-LRu{CO) 4 formed by reacting SiO 2 with C(EtO)3SiCH2CH2PP i ]Ru

  18. 4-{2-[2-(4-Formyl-phen-oxy)eth-oxy]eth-oxy}benzaldehyde.

    PubMed

    Ma, Zhen; Cao, Yiqun

    2011-06-01

    The title compound, C(18)H(18)O(5), was obtained by the reaction of 4-hy-droxy-benzaldehyde with bis-(2,2-dichloro-eth-yl) ether in dimethyl-formamide. In the crystal, the mol-ecule lies on a twofold rotation axis that passes through the central O atom of the aliphatic chain, thus leading to one half-mol-ecule being present per asymmetric unit. The carbonyl, aryl and O-CH(2)-CH(2) groups are almost coplanar, with an r.m.s. deviation of 0.030 Å. The aromatic rings are approximately perpendicular to each other, forming a dihedral angle of 78.31 sh;H⋯O hydrogen bonds and C-H⋯π inter-actions help to consolidate the three-dimensional network.

  19. Diethyl 2,2'-(ethane-1,2-diyldi-oxy)di-benzo-ate.

    PubMed

    Shi, Huaduan; Qin, Haisha; Ma, Zhen

    2014-05-01

    The mol-ecular title compound, C20H22O6, was obtained by the reaction of ethyl 2-hy-droxy-benzoate with 1,2-di-chloro-ethane. The mol-ecule lies on a twofold rotation axis which passes through the middle of the central ethyl-ene bridge. This group exhibits a gauche conformation with the corresponding O-C-C-O torsion angle being 73.2 (2)°. The C atoms of the carboxyl group, the aryl and the O-CH2 group are coplanar, with an r.m.s. deviation of 0.01 Å. The two aryl rings form a dihedral angle of 67.94 (4)°. The ester ethyl group is disordered over two sets of sites with an occupancy ratio of 0.59 (2):0.41 (2). The crystal packing is dominated by van der Waals forces.

  20. Toward a comprehensive understanding of solid-state core-level XPS linewidths: Experimental and theoretical studies on the Si2p and O1s linewidths in silicates

    NASA Astrophysics Data System (ADS)

    Bancroft, G. M.; Nesbitt, H. W.; Ho, R.; Shaw, D. M.; Tse, J. S.; Biesinger, M. C.

    2009-08-01

    High resolution X-ray Photoelectron Spectroscopy (XPS) core-level Si2p and O1s spectra of the nonconductors α-SiO2 (quartz) at 120 and 300 K and vitreous SiO2 at 300 K were obtained with a Kratos Axis Ultra XPS instrument (instrumental resolution of <0.4eV ) which incorporates a unique charge compensation system that minimizes differential charge broadening on nonconductors. The Si2p and O1s linewidths at 300 K ( ˜1.1 and ˜1.2eV , respectively) are similar for all silicates (and similar to previous thin film SiO2 spectra obtained previously), showing that differential charging does not contribute significantly to our spectra. At 120 K, there is a small decrease (0.04 eV) in the Si2p linewidth of α-SiO2 , but no measurable decrease in O1s linewidth. The O1s lines are generally and distinctly asymmetric. We consider all possible sources of line broadening and show that final state vibrational broadening (FSVB) and phonon broadening are the major causes of the broad and asymmetric lines. Previous high resolution gas phase XPS studies have identified large FSVB contributions to the Si2p spectra of SiCl4 , SiF4 , and Si(OCH3)4 molecules, and this vibrational structure leads total Si2p3/2 linewidths of up to ˜0.5eV , even with individual peak linewidths of <0.1eV . The Si atom of Si(OCH3)4 is an excellent analog for Si in crystalline SiO2 because the Si-O bond lengths and symmetric stretch frequencies are similar in both compounds. Similar vibrational contributions to the Si2p and O1s spectra of solid silicates are anticipated if the Si2p and O1s core-hole states produce similar changes to the Si-O bond length in both phases. To investigate the possibility, Car-Parrinello molecular dynamics calculations were performed and show that changes to Si-O bond lengths between ion and ground states (Δr) for both Si2p and O1s hole states are similar for both crystalline SiO2 and gaseous Si(OCH3)4 . Δr are -0.04Å for Si2p and ˜+0.05Å for O1s in both compounds. Indeed, the